Insulating film pattern forming method and semiconductor device

Abstract

The present invention provides a method for forming an insulating film pattern, including the steps of: providing a substrate including two or more different dielectric film regions; selectively forming a blocking film on the substrate to include a first region where a blocking film is formed and a second region where no blocking film or a relatively small amount of blocking film is formed; selectively forming an insulating film on the second region; and etching a portion of an upper portion of the insulating film.

Description

[Technical Field]

[0001] The present invention relates to a method for forming an insulating film pattern and a semiconductor device. [Background technology]

[0002] Silicon-based semiconductor devices have become dominant in the mass production of nanostructures, thanks to the dramatic advances in 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 complex process steps, such as applying photoresist (PR) on a thin film, heat treatment, pattern mask alignment, PR patterning by exposure, and etching the underlying thin film using the PR pattern. As a result, the smaller the pattern size, the longer the process time and cost required.

[0004] In particular, for ultra-fine patterning of less than 10 nm, the introduction of extreme ultraviolet (EUV) exposure equipment, a new light source, requires enormous costs of over several million dollars. However, technical issues such as variations in pattern linewidth (critical dimension, CD) and overlay, pattern loading effects, surface roughness (line edge roughness (LER) and line width roughness (LWR)), and low pellicle efficiency are limiting the ultra-fine and precise patterning.

[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 that can reduce process time and costs by simplifying process steps. Area-Selective Atomic Layer Deposition (AS-ALD, also known as ASD), which effectively utilizes the surface reaction characteristics of the ALD process and can form precise thin films with atomic-level thickness in a bottom-up manner in selective areas on multicolor 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 a thin film only on the growth area through selective reaction between the precursor and reactor used in the subsequent ALD deposition process after selectively modifying the surface of the substrate by modifying the surface properties of the substrate. Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention aims to provide a method for forming an insulating film pattern that can obtain highly uniform, high-density monomolecular selective blocking films and insulating films using dry techniques such as atomic layer deposition.

[0008] In addition, while the conventional dip-coating method for forming a barrier film requires several hours, this technology can selectively form a barrier film and an insulating film within a few minutes using the same insulating film forming equipment without external exposure, thereby providing an insulating film pattern forming method that offers 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 excellent selectivity and aspect ratio through an etching process and a repeating process. The above and additional problems are described in detail below.

[0010] As a means to solve the above problems, The present invention provides a method for forming an insulating film pattern, including the steps of: providing a substrate including two or more different dielectric film regions; selectively forming a blocking film on the substrate to include a first region where a blocking film is formed and a second region where no blocking film or a relatively small amount of blocking film is formed; selectively forming an insulating film on the second region; and etching a portion of an upper portion of the insulating film. The barrier film precursor used in the selective formation of the barrier film may be a precursor represented by the following Formula 1 or Formula 2:

[0011] [Chemical formula 1] JPEG2025540945000002.jpg35170 [Chemical formula 2] JPEG2025540945000003.jpg36170

[0012] (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 with halogen;

[0013] 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 other types of dielectric film regions and a silicon oxide insulating film formed on the substrate, wherein 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 the silicon oxide insulating film is formed in a relatively small amount, and the difference in thickness between the silicon oxide insulating film formed on the first region and the silicon oxide insulating film formed on the second region is 4.5 nm or more. [Effects of the Invention]

[0015] The present invention uses dry techniques such as atomic layer deposition to form the barrier film, which allows for the production of a highly uniform, high-density monomolecular barrier film.

[0016] In addition, while the conventional dip-coating method for forming a barrier film requires several hours, the present invention can form a barrier film within a few minutes using the same insulating film forming equipment without external exposure, thereby achieving cost and quality advantages.

[0017] In addition, it is possible to 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. Furthermore, by adding an etching process and repeating the process, a semiconductor device having an insulating film pattern with excellent selectivity and aspect ratio can be obtained. The above and additional effects will be described in detail below. [Brief explanation of the drawings]

[0018] [Figure 1] 1A to 1C are process flow diagrams illustrating a method for forming an insulating film pattern according to an embodiment of the present invention. [Figure 2] 1A and 1B are diagrams showing an increase in selectivity and aspect ratio of an insulating film by repeating a process of forming an insulating film pattern according to an embodiment of the present invention; BEST MODE FOR CARRYING OUT THE INVENTION

[0019] Before describing the present invention in detail below, it is to 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 claims, unless otherwise stated, the words "comprise", "comprises", 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 this specification and claims, the term "aryl" refers to a C5-50 aromatic hydrocarbon ring group, including aromatic rings such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, triphenyllenyl, perylenyl, chrysenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzochrysenyl, anthracenyl, stilbenyl, and pyrenyl; and "heteroaryl" refers to a C2-50 aromatic ring containing at least one heteroatom, including, for example, pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindolyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, and benzothiophene. 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, unless otherwise defined, Arx (where x is an integer) means a substituted or unsubstituted C6 to C50 aryl group or a substituted or unsubstituted C2 to C50 heteroaryl group; Lx (where x is an integer) means a direct bond, a substituted or unsubstituted C6 to C50 arylene group, or a substituted or unsubstituted C2 to C50 heteroarylene group; and Rx (where x is an integer) means, unless otherwise defined, hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 sulfide group, substituted or unsubstituted C6 to C50 aryl group, or substituted or unsubstituted C2 to 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, or C1-C30 alkyl group, C1-C30 alkylsulfinyl group, C1-C30 alkylsulfonyl group, C1-C30 alkylsulfanyl group, C1-C12 fluoroalkyl group, C2-C30 alkenyl group, C1-C30 alkoxy group, C1-C12 It may mean, but is not limited to, being substituted with one or more groups selected from the group consisting of an N-alkylamino group, a C2-C20 N,N-dialkylamino group, a substituted or unsubstituted C1-C30 sulfide group, a C1-C6 N-alkylsulfamoyl group, a C2-C12 N,N-dialkylsulfamoyl group, a C0-C30 silyl group, a C3-C20 cycloalkyl group, a C3-C20 heterocycloalkyl group, a C6-C50 aryl group, and a C3-C50 heteroaryl group. Furthermore, throughout this specification, the same symbols 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 embodiments unless clearly indicated to the contrary. Hereinafter, embodiments of the present invention and the effects thereof will be described.

[0025] The present invention will be described in detail below.

[0026] As shown in FIG. 1, a method for forming an insulating film pattern according to one embodiment of the present invention includes the steps of: providing a substrate including two or more different dielectric film regions; selectively forming a blocking film on the substrate to include a first region where a blocking film is formed and a second region where no blocking film or a relatively small amount of blocking film is formed; selectively forming an insulating film on the second region; and etching a portion of an upper portion of the insulating film. Specifically, the insulating film may be a silicon oxide insulating film.

[0027] After forming the blocking layer, the difference in water contact angle between the first region and the second region may be in the range of 7 to 50 degrees (Deg), specifically, in the range of 7 to 40 degrees (Deg), allowing the insulating film to be formed with high selectivity within this range.

[0028] After selectively forming the blocking layer, the method may further include forming a silicon oxide insulating layer on a second region where the blocking layer is not formed or where the blocking layer is formed in a relatively small amount. Here, the term "selective" means both a case where only one of them is completely selected and a case where one of them is relatively more selective than the other.

[0029] The surfaces of the other two or more dielectric film regions of the substrate may include an amine-terminated silicon region and a hydroxy-terminated silicon region. In a specific embodiment of the present invention, an insulating film pattern may be formed by selectively forming a blocking film between the amine-terminated silicon region and the hydroxy-terminated silicon region and then selectively forming an insulating film. The amine-terminated silicon region may be a silicon nitride film, and the hydroxy-terminated silicon region may be a silicon oxide film.

[0030] Meanwhile, to further enhance 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. Such pretreatment increases the difference in water contact angle between the first region and the second region to within a range of 22 to 40 degrees, resulting in a significant difference in surface reactivity between the precursor used to form 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.

[0031] The substrate pretreatment step is not limited, but specific examples include the following methods. For example, the substrate may be immersed in an HF aqueous solution or thermally annealed in an HF gas atmosphere. For another example, the substrate may be thermally annealed in an N2, H2, ammonia, hydrazine, or a mixed gas atmosphere or plasma-treated therewith. The pretreatment consisting of the gas phase process described above can be carried out using a deposition apparatus such as ALD or CVD, and the pretreatment can be carried out at a substrate temperature in the 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 chemical vapor deposition (CVD) and atomic layer deposition (ALD). Specifically, the selective formation of the barrier film includes two steps: a step of supplying a precursor for forming the barrier film and a purge step, which can be repeated two or more times. The purge step uses an inert gas, which can be one or more of nitrogen (N), argon, neon, and helium.

[0033] The precursor for forming the barrier film used in the step of selectively forming the barrier film according to an embodiment of the present invention may be represented by the following Chemical Formula 1 or 2.

[0034] [Chemical formula 1] JPEG2025540945000004.jpg35170 [Chemical formula 2] JPEG2025540945000005.jpg33170

[0035] 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 with halogen;

[0036] 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.

[0037] When substituted, the substituent may be 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, a C1 to C30 alkyl group, a C1 to C30 alkylsulfinyl group, a C1 to C30 alkylsulfonyl group, a C1 to C30 alkylsulfanyl group, a C1 to C12 fluoroalkyl group, a C2 to C30 alkenyl group, a C1 to C30 alkoxy group, a C It may be substituted with one or more groups selected from the group consisting of a C1 to C12 N-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 C3 to C50 heteroaryl group. Specifically, at least one hydrogen bonded to the carbon of R may be substituted with a halogen. Specifically, the halogen may be fluorine.

[0038] Specifically, 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.

[0039] The step of forming the silicon oxide insulating layer on the second region where the blocking layer is not formed or is formed relatively less may be performed by sputtering, CVD (Chemical Vapor Deposition), ALD (Atomic Layer Deposition), or the like.

[0040] Specifically, in the step of forming the 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, chamber residue, 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.

[0041] Specifically, for example, in the case of a silicon oxide insulating film, the insulating film can be formed by repeating the four-step unit process of supplying a primary source (Si precursor), purging, supplying a secondary source (reactant), and purging, as in a typical ALD process. Furthermore, the insulating film formation process can be repeated until a film having a predetermined thickness is achieved. In addition, when the insulating film forming process cycle is repeatedly performed, a step of selectively forming the above-mentioned blocking film can be added in the middle of the cycle 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. Purging during the insulating film formation process may be performed using an inert gas, and the inert gas used in the step of selectively forming the blocking film may be used.

[0043] As described above, after selectively forming an insulating film on the second region where no blocking film is formed or where a relatively small amount of blocking film is formed, a portion of the upper portion of the insulating film is etched.

[0044] During the process of forming the insulating film, the blocking film may be damaged by oxidizing reactants, which may cause some insulating film to be deposited on the first region where the blocking film is formed.

[0045] Although it is possible to etch only the insulating film formed in the first region using a mask, this method requires the preparation of a separate mask and the alignment of the mask to the pattern, and therefore an etching process is performed to remove the insulating film formed in the first region, and then a portion of the upper part of the insulating film formed in the second region is also etched together. At this time, the blocking film that may remain in the first region can also be etched together.

[0046] Various etching methods can be used, including dry etching and wet etching. Specifically, dry etching can be gas phase etching using reactive gases such as NF3 and HF, or plasma etching using plasma such as hydrogen plasma or argon plasma. Wet etching can be performed using reactive solutions such as hydrofluoric acid and phosphoric acid. In the case of wet etching, a cleaning process using deionized water can be performed afterwards to remove the solution remaining on the substrate surface.

[0047] 2, the steps of selectively forming the blocking layer, selectively forming the insulating layer, and etching can be repeated one or more times. The number of repetitions is not limited, and they can be repeated until the desired thickness of the selective insulating layer pattern of the semiconductor device is reached. As shown in the experimental examples described below, repeating the process can increase the selectivity and significantly increase the aspect ratio of the insulating layer pattern.

[0048] Meanwhile, one embodiment of the present invention provides a semiconductor device including a substrate including two or more other types of dielectric film regions and a silicon oxide insulating film formed on the substrate, wherein the silicon oxide insulating film includes a first region in which the silicon oxide insulating film is selectively formed and a second region in which the silicon oxide insulating film is not formed or 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 4.5 nm or more, specifically 8.0 nm or more.

[0049] Here, the same configurations and structures are used as described above. In a 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 a highly selective insulating film pattern can be obtained without using a separate mask pattern, with a thickness difference of 4.5 nm or more. In particular, by repeating the process multiple times, the thickness difference of the insulating film can be increased to 8.0 nm or more.

[0050] 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.

[0051] <Experimental Example 1> Method for forming a barrier film In this experiment, a barrier film was formed by atomic layer deposition using the traveling method. The precursor for forming the barrier film was placed in a canister, and the canister temperature was maintained at a constant temperature between -20 and 100°C for stable supply.

[0052] The ALD process consisted of one cycle of [insertion of precursor for forming barrier film - purge], and high-purity nitrogen (300 sccm) was used as the purge gas. The cycle was repeated 1 to 100 times as necessary. Si3N4 and SiO2 wafers were used as substrates, with or without HF aqueous solution treatment. The substrate temperature was adjusted between 25 and 300°C during the experiment. The barrier film formation results were confirmed using a water contact angle analyzer, and the results are shown in Table 1 below.

[0053] [Table 1]

[0054] 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, in the case of Comparative Example 1, which has one aldehyde group, an alkyl group with 10 or more carbon atoms, and no fluorine substituent, the contact angle difference is relatively small at 6.6 degrees (Deg).

[0055] It is also clear that by pretreating the substrate, the difference in contact angle can be significantly increased to 22 degrees (Deg) or more, specifically to the range of 22 to 40 degrees (Deg), compared to when the substrate is not pretreated.

[0056] <Experimental Example 2> Silicon oxide insulating film formation In this experiment, a traveling atomic layer deposition method 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.

[0057] The ALD process consisted of one cycle of [Si precursor injection - purge - reactant injection - purge], with high-purity nitrogen used as the purge gas. The cycle was repeated 1 to 200 times until a certain thickness was reached, and a barrier film deposition process could be added during this period. The substrates used were Si3N4 and SiO2 wafers with the barrier film formed in Experimental Example 1. The substrate temperature was adjusted between 25 and 300°C during the experiment. The film thickness was measured using an ellipsometer, and the results are shown in Table 2.

[0058] [Table 2]

[0059] 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 0.3 nm insulating film thickness difference in Comparative Example 3, where no blocking film was formed. Also, in the case of Comparative Example 4, which has one aldehyde group, an alkyl group with 10 or more carbon atoms, and no fluorine substituent, the insulating film thickness difference is relatively small at 0.7 nm.

[0060] It is also clear that by pretreating the substrate, the difference in insulating film thickness can be significantly increased to 2.2 nm or more, specifically to a range of 2.8 nm to 5.0 nm, compared to when the substrate is not pretreated.

[0061] <Experimental Example 3> Selective deposition method of silicon insulating film using the process of forming a barrier film, depositing an insulating film, and etching The method for forming a barrier film was the same as in Experimental Example 1, except that the substrate was pretreated with an HF aqueous solution and then a barrier film was selectively formed.Then, the method for forming a silicon oxide insulating film was the same as in Experimental Example 2, except that the insulating film formation process cycle was halved.

[0062] After that, an etching process was performed using low-concentration hydrofluoric acid. During low-concentration hydrofluoric acid etching, a wet etching process using a hydrofluoric acid solution was performed, and after etching, the hydrofluoric acid solution was removed and the surface was cleaned using deionized water (DI water). The concentration of the hydrofluoric acid solution was 0.1 Vol%. Etching proceeded for 7 seconds, and surface cleaning using deionized water proceeded for 3 seconds. Etching was continued until the SiO2 insulating film deposited in the area where the blocking film had been formed was completely removed. The presence or absence of remaining insulating film was confirmed by the SiO2 insulating film thickness, and the thin film thickness was measured using an ellipsometer.

[0063] The barrier film deposition-insulating film deposition-etching process was performed in the above three steps in order, and each cycle consisted of completing these three steps in sequence. In the experimental example, the cycle was repeated a total of six times. The film thickness was measured using an ellipsometer, and the results are shown in Table 3.

[0064] [Table 3]

[0065] As shown in Table 3 above, when a blocking layer is formed and an etching process is added, the thickness difference of the insulating film increases from 1.5 nm to 3.1 nm, 4.7 nm, 5.7 nm, 6.7 nm, and 8.0 nm as the process is repeated, confirming that an ultra-fine pattern with a high aspect ratio can be realized.

Claims

1. providing a substrate including two or more different dielectric film regions; selectively forming a blocking layer on the substrate to include a first region where the blocking layer is formed and a second region where the blocking layer is not formed or is formed in a relatively small amount; selectively forming an insulating film on the second region; and The method for forming an insulating film pattern includes the step of etching a part of an upper portion of the insulating film.

2. 2. The insulating film pattern forming method according to claim 1, wherein the insulating film is a silicon oxide insulating film.

3. 2. The method of claim 1, wherein after the step of forming the blocking layer, a difference in water contact angle between the first region and the second region is in the range of 7 to 50 degrees.

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

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

6. The pre-treatment step includes:

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

7. The pre-treatment step includes: N ２ , H ２ 4. The method for forming an insulating film pattern according to claim 3, wherein the method is carried out by thermal annealing or plasma treatment in an atmosphere of ammonia, hydrazine or a mixed gas thereof.

8. The pre-treatment step includes:

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

9. 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.

10. The step of forming the insulating film comprises:

2. The method for forming an insulating film pattern according to claim 1, wherein sputtering, CVD (Chemical Vapor Deposition), or ALD (Atomic Layer Deposition) is used.

11. The precursors used to form the silicon oxide insulating film include 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.

12. 2. The insulating film pattern forming method according to claim 1, wherein the etching step etches the insulating film formed in the first region together.

13. 13. The method of claim 12, wherein the etching step also etches the blocking film formed in the first region.

14. selectively forming the blocking film; selectively forming the insulating film; and 2. The method for forming an insulating film pattern according to claim 1, wherein the etching step is further repeated one or more times.

15. 2. The method of claim 1, wherein a precursor for forming a blocking film used in the step of selectively forming the blocking film is represented by the following Chemical Formula 1 or 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 with 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.

16. Examples of the substituent include deuterium, halogen, amino group, cyano group, nitrile group, nitro group, nitroso group, sulfamoyl group, isothiocyanate group, thiocyanate group, carboxyl 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 16. The precursor according to claim 15, wherein at least one of the N-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 C3 to C50 heteroaryl group.

17. a substrate including two or more different types of dielectric film regions; a silicon oxide insulating film formed on the substrate, The silicon oxide insulating film includes a first region in which the silicon oxide insulating film is selectively formed and a second 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 the difference in thickness between the silicon oxide insulating film formed on the first region and the silicon oxide insulating film formed on the second region is 4.5 nm or more.

18. 18. The semiconductor device of claim 17, wherein the difference in thickness between the silicon oxide insulating films formed on the first region and the second region is 8.0 nm or more.

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