Method for forming insulating film pattern, precursor for use in pattern formation, and semiconductor device

Abstract

The present invention provides a method for forming an insulating film pattern, comprising the steps of providing a substrate including two or more different types of dielectric film regions, and selectively forming a blocking film on the substrate to include a first region in which a blocking film is formed and a second region in which no blocking film is formed or is formed in a relatively small amount, wherein a difference in water contact angle between the first region and the second region is within a range of 7 to 50 degrees (Deg).

Description

[Technical field]

[0001] The present invention relates to a method for forming an insulating film pattern, a precursor used in the pattern formation, and a semiconductor device. [Background technology]

[0002] Silicon-based semiconductor devices have become predominantly used in processes that allow mass production of nanostructures, with the dramatic development of traditional top-down patterning techniques and the continuous reduction in fine line widths achieved through three-dimensional structuring.

[0003] Conventional top-down optical lithography involves a variety of complicated process steps, such as applying photoresist (PR) on a thin film, heat treatment, pattern mask alignment, PR patterning by exposure, and etching the lower thin film using the PR pattern. As a result, the smaller the pattern size, the more time and cost required for processing.

[0004] In particular, in order to form ultra-fine patterns of 10 nm or less, it is costing millions of dollars to introduce extreme ultraviolet (EUV) exposure equipment, a new light source. However, technical issues such as unevenness in pattern line width (critical dimension, CD) and overlay, pattern loading effect, surface roughness (line edge roughness (LER), line width roughness (LWR)), and low pellicle efficiency are limiting the ultra-fine and precise pattern formation.

[0005] Therefore, a new patterning paradigm technology is needed that can selectively and precisely form patterns in desired areas within multidimensional structures of 10 nm or less and reduce process time and costs by simplifying process steps. Area-Selective Atomic Layer Deposition (AS-ALD, aka ASD), which effectively utilizes the surface reaction characteristics of the ALD process and can form precise thin films with atomic-level thicknesses in a bottom-up manner in selective areas on top of multi-color patterns (i.e., patterns with various base layer materials), is being researched as a next-generation alternative patterning process.

[0006] Therefore, the AS-ALD process is a method that can create ultrafine nanostructure patterns by selectively depositing thin films only on growth areas through selective reaction between the precursors and reactor used in the subsequent ALD deposition process after selectively modifying the surface of the substrate and modifying the substrate surface properties. Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a method for forming an insulating film pattern, which can obtain a highly uniform and high-density monomolecular selective blocking film and insulating film by using a dry technique such as atomic layer deposition.

[0008] In addition, compared to the conventional barrier film formation method, a dip-coating method, which requires at least several hours, the present technology can selectively form a barrier film and an insulating film within a few minutes in the same insulating film formation equipment without external exposure, and therefore aims to provide a method for forming an insulating film pattern that can obtain cost and quality advantages.

[0009] Another object of the present invention is to provide a method for forming an insulating film pattern, which can form an insulating film pattern with excellent selectivity on two or more types of dielectric films, such as silicon nitride and silicon oxide, without using a separate mask, and a precursor for forming a blocking film used in the process. Another object of the present invention is to provide a semiconductor device having an insulating film pattern with high selectivity. The above problems and additional problems are described in detail below.

[0010] As a means for solving the above problems, The present invention provides a method for forming an insulating film pattern, comprising the steps of providing a substrate including two or more different types of dielectric film regions, and selectively forming a blocking film on the substrate to include a first region in which a blocking film is formed and a second region in which no blocking film is formed or is formed in a relatively small amount, wherein a difference in water contact angle between the first region and the second region is within a range of 7 to 50 degrees (Deg).

[0011] The present invention also provides a precursor for selectively forming a blocking film on a substrate including two or more different types of dielectric film regions, the precursor being represented by the following Chemical Formula 1 or Chemical Formula 2:

[0012] [Chemical formula 1] JPEG2025501906000002.jpg39163[Chemical formula 2] JPEG2025501906000003.jpg34163

[0013] (In the above Chemical Formula 1, R is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 sulfide group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C7-C50 aralkyl group, or a substituted or unsubstituted C2-C50 heteroaryl group, with the proviso that when the alkyl group has 10 or more carbon atoms, one or more hydrogen atoms are substituted by halogen; L is a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C1-C30 alkyleneoxy group, a substituted or unsubstituted C1-C30 sulfide group, a substituted or unsubstituted C3-C50 cycloalkylene group, a substituted or unsubstituted C6-C50 arylene group, a substituted or unsubstituted C2-C50 heteroarylene group, or a combination thereof.

[0014] The present invention also provides a semiconductor device including a substrate including two or more different types of dielectric film regions, and a silicon oxide insulating film formed on the substrate, the silicon oxide insulating film including a second region in which the silicon oxide insulating film is selectively formed, and a first region in which no silicon oxide insulating film is formed or in which the silicon oxide insulating film is formed in a relatively small amount, and the thickness difference between the silicon oxide insulating film formed on the first region and the silicon oxide insulating film formed on the second region is 0.8 nm or more. Effect of the Invention

[0015] The present invention uses dry techniques such as atomic layer deposition to form the barrier film, and therefore can provide a highly uniform and dense monomolecular barrier film.

[0016] In addition, compared to the conventional barrier film formation method, which requires at least several hours, the present invention can form a barrier film within a few minutes using the same insulation film formation equipment without external exposure, thereby providing cost and quality advantages. In addition, an insulating film pattern can be formed with excellent selectivity on two or more types of dielectric films such as silicon nitride and silicon oxide without using a separate mask.

[0017] The above effects and additional effects are described in detail below. [Brief description of the drawings]

[0018] [Figure 1] 1A to 1C are process flow diagrams of a method for forming an insulating film pattern according to an embodiment of the present invention. BEST MODE FOR CARRYING OUT THE INVENT

[0019] Before describing the present invention in detail below, it should be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention, which is limited only by the appended claims. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art, unless otherwise defined.

[0020] Throughout this specification and the claims, unless otherwise indicated, the words comprise, comprise, and comprising are used to mean the inclusion of the stated item, step or group of items and steps and are not used to mean the exclusion of any other item, step or group of items or groups of steps.

[0021] Throughout the present specification and claims, the term "aryl" refers to an aromatic hydrocarbon ring group having C5 to C50, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, triphenylenyl, perylenyl, chrysenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzochrysenyl, anthracenyl, stilbenyl, pyrenyl, and the like, and "heteroaryl" refers to an aromatic ring having C2 to C50 containing at least one hetero element, such as pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindolyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, benzothiophene, and the like. It can mean including heterocyclic groups formed from a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, an indole ring, a quinoline ring, an acridine ring, a pyrrolidine ring, a dioxane ring, a piperidine ring, a morpholine ring, a piperazine ring, a carbazole ring, a furan ring, a thiophene ring, an oxazole ring, an oxadiazole ring, a benzofuran ring, a thiazole ring, a thiadiazole ring, a benzothiophene ring, a triazole ring, an imidazole ring, a benzimidazole ring, a pyran ring, a dibenzofuran ring, or the like.

[0022] In the chemical formulae, Arx (where x is an integer) means, unless otherwise defined, a substituted or unsubstituted C6-C50 aryl group or a substituted or unsubstituted C2-C50 heteroaryl group; Lx (where x is an integer) means, unless otherwise defined, a direct bond, a substituted or unsubstituted C6-C50 arylene group, or a substituted or unsubstituted C2-C50 heteroarylene group; and Rx (where x is an integer) means, unless otherwise defined, hydrogen, deuterium, halogen, a nitro group, a nitrile group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 sulfide group, a substituted or unsubstituted C6-C50 aryl group, or a substituted or unsubstituted C2-C50 heteroaryl group.

[0023] Throughout this specification and the claims, the term "substituted or unsubstituted" means any of deuterium, halogen, amino group, cyano group, nitrile group, nitro group, nitroso group, sulfamoyl group, isothiocyanate group, thiocyanate group, carboxyl group, carbonyl group, C1 to C30 alkyl group, C1 to C30 alkylsulfinyl group, C1 to C30 alkylsulfonyl group, C1 to C30 alkylsulfanyl group, C1 to C12 fluoroalkyl group, C2 to C30 alkenyl group, C1 to C30 alkoxy group, C1 to C12 aryl ... It may mean that it is substituted or unsubstituted with one or more groups selected from the group consisting of an N-alkylamino group of C2 to C20, an N,N-dialkylamino group of C2 to C20, a substituted or unsubstituted sulfide group of C1 to C30, an N-alkylsulfamoyl group of C1 to C6, an N,N-dialkylsulfamoyl group of C2 to C12, a silyl group of C0 to C30, a cycloalkyl group of C3 to C20, a heterocycloalkyl group of C3 to C20, an aryl group of C6 to C50, and a heteroaryl group of C3 to C50, but is not particularly limited thereto. In addition, the same symbols throughout this specification may have the same meaning unless otherwise specified.

[0024] On the other hand, various embodiments of the present invention may be combined with any other embodiment unless clearly indicated to the contrary. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention and their effects will be described.

[0025] The present invention will be described in detail below. A method for forming an insulating film pattern according to one embodiment of the present invention includes providing a substrate including two or more different types of dielectric film regions, and selectively forming a blocking film on the substrate to include a first region in which a blocking film is formed and a second region in which no blocking film is formed or a relatively small amount of blocking film is formed.

[0026] The difference in water contact angle between the first region and the second region may be within a range of 7 to 50 degrees (Deg), specifically within a range of 7 to 40 degrees (Deg), within which an insulating film can be formed with high selectivity.

[0027] After the step of selectively forming the barrier layer, the method may further include the step of forming a silicon oxide insulating layer on a second region where the barrier layer is not formed or is formed in a relatively small amount. Here, the term "selective" includes both a case where only one is completely selected and a case where one has a relatively higher selectivity than the other.

[0028] The surfaces of the two or more different dielectric film regions of the substrate may include an amine-terminated silicon region and a hydroxyl-terminated silicon region. In a specific embodiment of the present invention, the amine-terminated silicon region and the hydroxyl-terminated silicon region are differentiated from each other, and a blocking film is selectively formed, followed by selectively forming an insulating film to form an insulating film pattern. The amine-terminated silicon region is specifically a silicon nitride film, and the hydroxyl-terminated silicon region is specifically a silicon oxide film.

[0029] Meanwhile, in order to further increase the selectivity, the method may further include a step of pretreating the substrate including the dielectric film region before the step of selectively forming the barrier film. By carrying out the pretreatment in this manner, the difference in water contact angle between the first region and the second region increases to within a range of 22 to 40 degrees (Deg), and a large difference in surface reactivity occurs between the precursor used for forming the barrier film and the two regions. The difference in surface reactivity results in the selective formation of a barrier film in the first region and the selective formation of an insulating film in the second region.

[0030] The step of pretreating the substrate is not limited, but specifically includes the following methods. One example is immersing the substrate in an HF aqueous solution or thermally annealing in an HF gas atmosphere. Another example is thermal annealing the substrate in an N2, H2, ammonia, hydrazine, or mixed gas atmosphere or plasma treatment thereof.

[0031] The pretreatment consisting of the above gas phase process can be carried out using a deposition apparatus such as ALD or CVD, and the pretreatment can be carried out at a substrate temperature within a range of 0 to 800°C.

[0032] The selective formation of the barrier film can be achieved by various methods using gas-phase reactions such as CVD (Chemical Vapor Deposition) and ALD (Atomic Layer Deposition). Specifically, the selective formation of the barrier film includes a step of supplying a precursor for forming the barrier film and a step of purging, which can be repeated two or more times. The purging step uses an inert gas, which can be one or more of nitrogen (N2), argon, neon, and helium. The precursor for forming a barrier film according to an embodiment of the present invention may be represented by the following Formula 1 or Formula 2.

[0033] [Chemical formula 1] JPEG2025501906000004.jpg39163[Chemical formula 2] JPEG2025501906000005.jpg33163

[0034] In the above Chemical Formula 1, R is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 sulfide group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C7-C50 aralkyl group, or a substituted or unsubstituted C2-C50 heteroaryl group, with the proviso that when the alkyl group has 10 or more carbon atoms, one or more hydrogen atoms are substituted by halogen; L is a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C1-C30 alkyleneoxy group, a substituted or unsubstituted C1-C30 sulfide group, a substituted or unsubstituted C3-C50 cycloalkylene group, a substituted or unsubstituted C6-C50 arylene group, a substituted or unsubstituted C2-C50 heteroarylene group, or a combination thereof.

[0035] In the case where the substituent is present, examples of the substituent include deuterium, halogen, an amino group, a cyano group, a nitrile group, a nitro group, a nitroso group, a sulfamoyl group, an isothiocyanate group, a thiocyanate group, a carboxyl group, an alkyl group having C1 to C30, an alkylsulfinyl group having C1 to C30, an alkylsulfonyl group having C1 to C30, an alkylsulfanyl group having C1 to C12, a fluoroalkyl group having C2 to C30, an alkenyl group having C2 to C30, an alkoxy group having C1 to C30, a C It may be substituted with one or more groups selected from the group consisting of an N-alkylamino group having 1 to C12, an N,N-dialkylamino group having 2 to C20, a sulfide group having 1 to C30, an N-alkylsulfamoyl group having 1 to C6, an N,N-dialkylsulfamoyl group having 2 to C12, a silyl group having 3 to C30, a cycloalkyl group having 3 to C20, a heterocycloalkyl group having 3 to C20, an aryl group having 6 to C50, and a heteroaryl group having 2 to C50.

[0036] Specifically, at least one hydrogen bonded to the carbon of R may be replaced with a halogen. Specifically, the halogen may be fluorine.

[0037] Specifically, the R may be a C1 to C20 alkyl group substituted with one or more fluorine atoms, or a C6 to C50 aryl group substituted with one or more fluorine atoms.

[0038] The step of forming a silicon oxide insulating layer on the second region where the barrier layer is not formed or is formed relatively less may be performed using a sputtering method, a CVD (Chemical Vapor Deposition) method, an ALD (Atomic Layer Deposition) method, or the like.

[0039] Specifically, in the step of forming the silicon oxide insulating film, the oxygen source may be one or more selected from the group consisting of oxygen, hydrogen peroxide, ozone, nitric oxide, water plasma, oxygen plasma, residues in the chamber, or oxygen, and the nitrogen source may be one or more selected from the group consisting of ammonia, hydrazine, alkylhydrazine, dialkylhydrazine, nitrogen plasma, plasma of a mixed gas of nitrogen and hydrogen, ammonia plasma, plasma of a mixed gas of ammonia and hydrogen, and mixtures thereof.

[0040] The formation of silicon oxide insulating film can be performed by repeating the four-step unit process of primary source (Si precursor) supply-purge-secondary source (reactant) supply-purge, as in the normal ALD process. Furthermore, the dielectric film formation process can be cycled until a film with a predetermined thickness is achieved.

[0041] In addition, when the silicon oxide insulating film forming process cycle is repeatedly performed, a step of selectively forming the above-mentioned blocking film may be added in the middle of the cycle in order to increase the selectivity.

[0042] When a Si precursor is used as the primary raw material, the Si precursor may be, for example, a silane, and the silane may be specifically selected from SiH4, diisopropylaminosilane (DIPAS), bis-diethylaminosilane (BDEAS), tris(dimethylamino)silane (TDMAS), bis(t-butylamino)silane (BTBAS), or a combination thereof. The reactant used as the secondary raw material may be the oxygen source or nitrogen source exemplified above.

[0043] The purging during the silicon oxide insulating film forming process may be performed using an inert gas, and the inert gas used in the selective formation of the barrier film may be used. During the silicon oxide insulating film forming process, the barrier film may be removed during the process, or may remain entirely or partially.

[0044] Meanwhile, one embodiment of the present invention provides a semiconductor device including a substrate including two or more different types of dielectric film regions and a silicon oxide insulating film formed on the substrate, the silicon oxide insulating film including a second region in which the silicon oxide insulating film is selectively formed and a first region in which no silicon oxide insulating film is formed or a relatively small amount of silicon oxide insulating film is formed, and a thickness difference between the silicon oxide insulating film formed on the first region and the silicon oxide insulating film formed on the second region is 0.8 nm or more.

[0045] Here, the same configuration and structure are used as described above. In the semiconductor device according to an embodiment of the present invention, a silicon oxide insulating film is selectively formed in two or more dielectric film regions, and the thickness difference of the insulating film is 0.8 nm or more, so that a highly selective insulating film pattern can be obtained without using a separate mask pattern. In particular, since the selectivity during substrate pretreatment is excellent, the thickness difference of the insulating film can be increased to 2.2 nm or more.

[0046] The present invention will be described in more detail below with reference to specific examples. The following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples.

[0047] <Experimental Example 1> Method of forming a barrier film In this experimental example, a traveling atomic layer deposition method was used to form a barrier film. The precursor for forming the barrier film was placed in a canister and the canister temperature was kept constant at -20 to 100°C for stable supply.

[0048] The ALD process consisted of one cycle of [insertion of precursor for forming barrier film-purge], and high purity nitrogen (300sccm) was used as the purge gas. The cycle was repeated 1 to 100 times as necessary. The substrates used were Si3N4 and SiO2 wafers, which were either treated with an HF aqueous solution or omitted this treatment. The substrate temperature was adjusted between 0 and 500°C during the experiment. The results of barrier film formation were confirmed using a water contact angle analyzer, and the results are shown in Table 1 below.

[0049] [Table 1]

[0050] As shown in Table 1, when a blocking film is formed as in Examples 1 to 7, the contact angle difference is 8 degrees (Deg) or more, specifically in the range of 8.6 to 13.8 degrees (Deg), which is significantly larger than the contact angle difference of 3.1 degrees (Deg) in Comparative Example 1 where a blocking film is not formed. Also, it can be seen that in the case of Comparative Example 1 where there is one aldehyde group, the alkyl group has 10 or more carbon atoms, and there is no fluorine substituent, the contact angle difference is relatively small at 6.6 degrees (Deg).

[0051] It is also clear that by pretreating the substrate, the contact angle difference can be significantly increased to 22 degrees (Deg) or more, specifically to a range of 22 to 40 degrees (Deg), compared to when the substrate is not pretreated.

[0052] <Experimental Example 2> Silicon oxide insulating film formation In this experimental example, the traveling atomic layer deposition was introduced, and SiO2 film formation evaluation was carried out using DIPAS (diisopropylaminosilane) as the Si precursor and ozone (O3) as the reactant. The Si precursor was placed in a canister and used without additional heating.

[0053] The ALD process consisted of one cycle of [Si precursor injection-purge-reactant injection-purge], and high purity nitrogen was used as the purge gas. The cycle was repeated 1 to 200 times until a certain thickness was reached, during which a barrier film deposition process could be added. The substrates used were Si3N4 and SiO2 wafers with the barrier film formed thereon in Experimental Example 1. The substrate temperature was adjusted between 25 and 300°C. The thickness of the thin film was measured using an ellipsometer, and the results are shown in Table 2.

[0054] [Table 2]

[0055] As shown in Table 2, when a blocking film is formed as in Examples 8 to 14, the insulating film thickness difference is 0.8 nm or more, specifically in the range of 0.8 nm to 1.5 nm, which is significantly larger than the insulating film thickness difference of 0.3 nm in Comparative Example 3 where no blocking film was formed. Also, in the case of Comparative Example 4 where there is one aldehyde group, the alkyl group has 10 or more carbon atoms, and there is no fluorine substituent, the insulating film thickness difference is relatively small at 0.7 nm.

[0056] It is also clear that by pretreating the substrate, the insulating film thickness difference can be significantly increased to 2.2 nm or more, specifically to a range of 2.8 nm to 5.0 nm, compared to the case where the substrate is not pretreated.

Claims

1. Providing a substrate including two or more different dielectric film regions; 1. A method for forming an insulating film pattern, comprising: selectively forming a blocking layer on a substrate to include a first region having a blocking layer formed thereon and a second region having no blocking layer or a relatively small amount of blocking layer formed thereon, A method for forming an insulating film pattern, wherein a difference in water contact angle between the first region and the second region is within a range of 7 to 50 degrees (Deg).

2. 2. The method of claim 1, further comprising forming a silicon oxide insulating film on a second region where the blocking film is not formed or is formed in a relatively small amount.

3. Before the selectively forming the blocking film, 2. The method of claim 1, further comprising the step of pretreating the substrate.

4. 4. The method for forming an insulating film pattern according to claim 3, wherein a difference in water contact angle between the first region and the second region is within a range of 22 to 40 degrees.

5. The step of pretreating the substrate comprises:

4. The method for forming an insulating film pattern according to claim 3, wherein the substrate is immersed in an aqueous HF solution or thermally annealed in an HF gas atmosphere.

6. The step of pretreating the substrate comprises:

4. The method for forming an insulating film pattern according to claim 3, wherein the method is carried out by thermal annealing in an atmosphere of N2, H2, ammonia, hydrazine or a mixed gas thereof or a plasma treatment thereof.

7. 2. The method for forming an insulating film pattern according to claim 1, wherein the surface of the dielectric film of the substrate includes an amine-terminated silicon region and a hydroxyl-terminated silicon region.

8. 2. The method for forming an insulating film pattern according to claim 1, wherein the dielectric film of the substrate includes a silicon nitride film region and a silicon oxide film region.

9. The step of forming the silicon oxide insulating film comprises:

3. The method for forming an insulating film pattern according to claim 2, wherein sputtering, CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition) is used.

10. The precursor used to form the silicon oxide insulating film is SiH ４ 3. The method for forming an insulating film pattern according to claim 2, wherein the silane is selected from the group consisting of diisopropylaminosilane (DIPAS), bis-diethylaminosilane (BDEAS), tris(dimethylamino)silane (TDMAS), bis(t-butylamino)silane (BTBAS), and combinations thereof.

11. A precursor for use in selectively forming a barrier film on a substrate containing two or more different dielectric film regions, comprising: The precursor is a precursor represented by the following chemical formula 1 or chemical formula 2: [Chemical formula 1] [Chemical formula 2] (In the above Chemical Formula 1, R is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 sulfide group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C7-C50 aralkyl group, or a substituted or unsubstituted C2-C50 heteroaryl group, provided that when the alkyl group has 10 or more carbon atoms, one or more hydrogen atoms are substituted by halogen; L is a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C1-C30 alkyleneoxy group, a substituted or unsubstituted C1-C30 sulfide group, a substituted or unsubstituted C3-C50 cycloalkylene group, a substituted or unsubstituted C6-C50 arylene group, a substituted or unsubstituted C2-C50 heteroarylene group, or a combination thereof.

12. The substituents are deuterium, halogen, an amino group, a cyano group, a nitrile group, a nitro group, a nitroso group, a sulfamoyl group, an isothiocyanate group, a thiocyanate group, a carboxyl group, an alkyl group of C1 to C30, an alkylsulfinyl group of C1 to C30, an alkylsulfonyl group of C1 to C30, an alkylsulfanyl group of C1 to C30, a fluoroalkyl group of C1 to C12, an alkenyl group of C2 to C30, an alkoxy group of C1 to C30, a N-alkyl group of C1 to C12, a methyl group of C2 to C30, a methyl ...

12. The precursor according to claim 11, wherein the alkyl group is at least one selected from the group consisting of an alkylamino group, a C2 to C20 N,N-dialkylamino group, a C1 to C30 sulfide group, a C1 to C6 N-alkylsulfamoyl group, a C2 to C12 N,N-dialkylsulfamoyl group, a C3 to C30 silyl group, a C3 to C20 cycloalkyl group, a C3 to C20 heterocycloalkyl group, a C6 to C50 aryl group, and a C2 to C50 heteroaryl group.

13. A substrate including two or more different types of dielectric film regions; A semiconductor device including a silicon oxide insulating film formed on the substrate, The silicon oxide insulating film includes a second region in which the silicon oxide insulating film is selectively formed, and a first region in which no silicon oxide insulating film is formed or in which a relatively small amount of silicon oxide insulating film is formed, and a thickness difference between the silicon oxide insulating films formed on the first region and the second region is 0.8 nm or more.

14. 14. The semiconductor device according to claim 13, wherein a difference in thickness between the silicon oxide insulating films formed on the first region and the second region is 2.2 nm or more.

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