Insulating film pattern forming method and semiconductor element

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; a step of selectively forming a shielding film on the substrate, the shielding film including a first region in which the shielding film is formed and a second region in which no or less shielding film is formed; a step of selectively forming an insulating film on the second region; and a step for etching a portion of the 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 Art

[0002] With the rapid development and three-dimensional structuring of existing top-down patterning technologies, semiconductor devices based on silicon materials have achieved continuous reduction in minimum line width, and thus have been used as the dominant method for mass production of nanostructures. Existing top-down optical lithography involves complex engineering steps such as coating a photoresist (PR) on a thin film, heat treatment, pattern mask alignment, patterning of the photoresist (PR) by exposure, and etching of the underlying thin film according to the photoresist (PR) pattern. Therefore, the smaller the pattern size, the more engineering time and cost are required.

[0003] In particular, to form ultra-fine patterns of less than 10 nm, it is necessary to invest more than several million dollars to introduce a new light source, i.e., extreme ultraviolet (EUV) exposure equipment. Moreover, due to technical problems such as non-uniformity of pattern line width (critical dimension, CD) and alignment (overlay), pattern loading effect, surface roughness (line edge roughness; LER, line width roughness; LWR), and low film efficiency, limitations are imposed on the ultra-fine and precise formation of patterns.

[0004] Therefore, there is a need for a new patterning paradigm technology that can selectively form precise patterns in a desired region within a multi-dimensional structure of less than 10 nm and save engineering time and cost by simplifying engineering steps. As an alternative to the next-generation patterning process, active research is being conducted on area-selective atomic layer deposition (AS-ALD, aka. ASD), which can form a precise thin film with an atomic-level thickness in a bottom-up manner in a selective region by effectively utilizing the surface reaction characteristics of atomic layer deposition (ALD) technology. Therefore, the area-selective atomic layer deposition (AS-ALD) process is a method for manufacturing ultra-fine nanostructure patterns by selectively modifying the surface properties of a substrate through surface modification of regions where growth is not required, and then selectively depositing a thin film only in the growth region through the selective reaction of a precursor used in a subsequent atomic layer deposition (ALD) process with a reactor. Summary of the Invention

[0005] Problems to be Solved by the Invention

[0006] An object of the present invention is to provide a method for forming an insulating film pattern capable of obtaining a very uniform and high-density single-molecule selective shielding film and insulating film by using a dry technique such as atomic layer deposition.

[0007] In addition, an object thereof is to provide a method for forming an insulating film pattern that can form a selective shielding film and an insulating film within a few minutes using the same insulating film forming equipment without external exposure, as compared with the problem that the conventional shielding film forming method, i.e., the dip-coating method, requires at least several hours, thereby achieving advantages in terms of cost and quality.

[0008] In addition, an object thereof is to provide a method for forming an insulating film pattern capable of forming an insulating film pattern with excellent selectivity on two or more types of dielectric films such as silicon nitride and silicon oxide without the need for a separate mask, and a precursor for forming a shielding film used in the process.

[0009] In addition, an object thereof is to provide a semiconductor device capable of providing an insulating film pattern with excellent selectivity and aspect ratio through an etching process and a repeating process.

[0010] Next, the above-described problems and additional problems will be described in detail.

[0011] Means for Solving the Problems

[0012] Specific means for solving the above-described problems are as follows.

[0013] The present invention provides a method for forming an insulating film pattern, comprising: providing a substrate including regions of two or more different types of dielectric films; selectively forming a shielding film on the substrate, the shielding film including a first region where a shielding film is formed and a second region where no shielding film or a relatively small amount of shielding film is formed; selectively forming an insulating film on the second region; and etching an upper part of the insulating film.

[0014] The shielding film precursor used in the step of selectively forming the shielding film may be a precursor represented by Chemical Formula 1 or Chemical Formula 2 below.

[0015] [Chemical Formula 1]

[0016]

[0017] [Chemical Formula 2]

[0018]

[0019] In the 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 thioether group, or a substituted or unsubstituted C1-C30 or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C7-C50 aralkyl group, or a substituted or unsubstituted C2-C50 heteroaryl group, wherein, when the alkyl group has 10 or more carbon atoms, it is an alkyl group in which one or more hydrogens are substituted by a halogen;

[0020] L is a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C1-C30 alkoxylene group, or a substituted or unsubstituted C1-C30 thioether 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.

[0021] In addition, the present invention provides a semiconductor device, comprising: 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 includes a first region selectively formed with a tin oxide insulating film and a second region where no or relatively less silicon oxide insulating film is formed, and the thickness difference of the silicon oxide insulating film formed on the first region and the second region is 4.5 nm or more.

[0022] Advantages of the Invention

[0023] The invention applies dry techniques such as atomic layer deposition to the formation of the shielding film, so a very uniform and high-density single-molecule shielding film can be obtained.

[0024] In addition, compared with the problem that the conventional shielding film formation method, i.e., the dip-coating method, requires at least several hours, the shielding film can be formed within a few minutes using the same insulating film forming equipment without external exposure, thereby achieving advantages in terms of cost and quality.

[0025] In addition, an insulating film pattern can be excellently selectively formed on two or more types of dielectric films such as silicon nitride and silicon oxide without the need for a separate mask.

[0026] In addition, a semiconductor device having an insulating film pattern with excellent selectivity and aspect ratio can be obtained through additional etching processes and repeating processes.

[0027] Next, the above-mentioned effects and additional effects will be described in detail. Description of the Drawings

[0028] Figure 1 Engineering flowchart of an insulating film pattern forming method according to an embodiment of the present invention;

[0029] Figure 2 Schematic diagram related to the selectivity and aspect ratio increase of an insulating film based on a repetitive process of an insulating film pattern forming method according to an embodiment of the present invention. Detailed implementation

[0030] Before the following detailed description of the present invention, it should be understood that the terms used in this specification are only for describing specific embodiments and are not intended to limit the scope of the present invention defined only by the appended patent application scope. Unless otherwise mentioned, the meanings of all technical terms and scientific terms used in this specification are the same as those generally understood by those with ordinary skills.

[0031] In all of this specification and the patent application scope, unless otherwise mentioned, the term "comprise" (comprise, comprises, comprising) is only used to indicate the inclusion of the mentioned objects, steps or a series of objects and steps, and does not mean excluding any other objects, steps or a series of objects or a series of steps.

[0032] In all of this specification and the claims, the term "aryl" refers to an aromatic hydrocarbon ring group of C5 - 50 containing aromatic rings such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, fluorenyl, phenanthryl, triphenylene, phenylene, yl, fluoranthenyl, benzofluorenyl, benzotriphenylene, benzo yl, anthryl, stilbenyl, and pyrenyl, and "heteroaryl" refers to an aromatic ring containing at least one hetero element of C2 - 50 such as a heterocyclic group composed of pyrrolyl, pyrazinyl, pyridyl, indolyl, isoindolyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, benzothienyl, dibenzothienyl, quinolinyl, isoquinolinyl, quinoxalinyl, oxazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, thienyl, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, indole ring, quinoline ring, acridine ring, pyrrolidine ring, dioxane ring, piperidine ring, morpholine ring, piperazine ring, oxazole ring, furan ring, thienyl ring, oxazole ring, oxadiazole ring, benzofuran ring, thiazole ring, thiadiazole ring, benzothienyl ring, triazole ring, imidazole ring, benzimidazole ring, pyran ring, dibenzofuran ring, etc.

[0033] In addition, in a chemical formula, unless otherwise clearly defined, Arx (where x is an integer) refers to a substituted or unsubstituted C6-C50 aryl group, or a substituted or unsubstituted C2-C50 heteroaryl group; Lx (where x is an integer) refers to a directly bonded, substituted or unsubstituted C6-C50 arylene group, or a substituted or unsubstituted C2-C50 heteroarylene group; and Rx (where x is an integer) refers to hydrogen, deuterium, a 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 thioether group, a substituted or unsubstituted C6-C50 aryl group, or a substituted or unsubstituted C2-C50 heteroaryl group.

[0034] In all of the present specification and claims, the term "substituted or unsubstituted" means substituted or unsubstituted by one or more groups selected from the group consisting of deuterium, a 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 carbonyl group, a C1-C30 alkyl group, a C1-C30 alkylsulfinyl group, a C1-C30 alkylsulfonyl group, a C1-C30 alkylsulfonate group, a C1-C12 fluoroalkyl group, a C2-C30 alkenyl group, a C1-C30 alkoxy group, a C1-C12 N-alkylamino group, a C2-C20 N,N-dialkylamino group, a substituted or unsubstituted C1-C30 thioether 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 heteroaryl group, etc. In addition, in all of the present specification, unless otherwise clearly mentioned, the same symbols may have the same meanings.

[0035] In addition, unless otherwise clearly stated to the contrary, multiple embodiments of the present invention may be combined with any other embodiment. Next, embodiments of the present invention and their effects will be described.

[0036] Next, the present invention will be described in detail.

[0037] As Figure 1 shown, an insulating film pattern forming method according to an embodiment of the present invention includes: a step of providing a substrate including two or more different types of dielectric film regions; a step of selectively forming a shielding film on the substrate, the shielding film including a first region where a shielding film is formed and a second region where no shielding film or a relatively small amount of shielding film is formed; a step of selectively forming an insulating film on the second region; and a step of etching an upper part of the insulating film.

[0038] Specifically, the insulating film may be a silicon oxide insulating film.

[0039] After the step of forming the shielding film, the difference in the water contact angle between the first region and the second region may be in the range of 7 to 50 degrees (Deg), specifically, it may be in the range of 7 to 40 degrees (Deg). Within this range, the insulating film can be formed with high selectivity.

[0040] After the step of selectively forming the shielding film, it may further include: a step of forming a silicon oxide insulating film on the second region where no shielding film is formed or where a relatively small amount of shielding film is formed.

[0041] Herein, the meaning of selectivity includes both the case of perfectly selecting only one party and the case where the selectivity of one party is relatively higher than that of the other party.

[0042] The two or more different types of 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 can be distinguished, so as to form an insulating film pattern by selectively forming an insulating film after selectively forming the shielding film. Specifically, the amine-terminated silicon region may be exemplified by a silicon nitride film, and the hydroxyl-terminated silicon region may be exemplified by a silicon oxide film.

[0043] Meanwhile, in order to further improve the selectivity, before the step of selectively forming the shielding film, it may further include: a step of pre-treating the substrate including the dielectric film region. By pre-treating in the above-described manner, the difference in the water contact angle between the first region and the second region will increase to the range of 22 to 40 degrees (Deg), thereby forming a large difference in the surface reactivity between the precursor for forming the shielding film and the two regions. The difference in surface reactivity will further selectively form the shielding film on the first region and selectively form the insulating film on the second region.

[0044] Specifically, the following method may be adopted in the step of pre-treating the substrate, but it is not limited thereto. As an example, the substrate can be dipped in an HF aqueous solution or thermally annealed in an HF gas environment. As another example, it can be performed by thermally annealing the substrate in an environment of N2, H2, ammonia, hydrazine or a mixed gas thereof or by performing plasma treatment on it.

[0045] In the pretreatment performed by the gas phase process, deposition equipment such as atomic layer deposition (ALD) or chemical vapor deposition (CVD) can be used, and the pretreatment can be carried out within a substrate temperature range of 0 to 800 °C.

[0046] In the step of selectively forming the shielding film, various methods using gas-phase reactions such as chemical vapor deposition (CVD) and atomic layer deposition (ALD) can be selected. Specifically, the step of selectively forming the shielding film may include a first step of supplying a precursor for forming the shielding film and a second step of purging, and these steps are repeated more than 2 rounds. The purging uses an inert gas, and the inert gas can be one or more of nitrogen (N2), argon, neon, and helium.

[0047] The precursor for forming the shielding film used in the step of selectively forming the shielding film according to an embodiment of the present invention can be represented by the following Chemical Formula 1 or the following Chemical Formula 2.

[0048] [Chemical Formula 1]

[0049]

[0050] [Chemical Formula 2]

[0051]

[0052] In 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 thioether group, or a substituted or unsubstituted C1-C30 or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C7-C50 aralkyl group, or a substituted or unsubstituted C2-C50 heteroaryl group. Among them, when the alkyl group has 10 or more carbon atoms, it is an alkyl group in which one or more hydrogens are substituted by halogens.

[0053] L is a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C1-C30 alkoxylene group, or a substituted or unsubstituted C1-C30 thioether 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.

[0054] In the case of substitution, as the substituent, it can be substituted by one or more groups selected from the group consisting of deuterium, halogen, amino, cyano, nitrile, nitro, nitroso, sulfamoyl, isothiocyanate, thiocyanate, carboxyl, C1-C30 alkyl, C1-C30 alkylsulfinyl, C1-C30 alkylsulfonyl, C1-C30 alkylsulfonate, C1-C12 fluoroalkyl, C2-C30 alkenyl, C1-C30 alkoxy, C1-C12 N-alkylamino, C2-C20 N,N-dialkylamino, C1-C30 thioether, C1-C6 N-alkylsulfamoyl, C2-C12 N,N-dialkylsulfamoyl, C3-C30 silyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C50 aryl, and substituted by one or more groups selected from the group consisting of heteroaryl and the like.

[0055] Specifically, one or more hydrogens bonded to carbon in the R can be substituted by halogen. Specifically, the halogen can be fluorine.

[0056] Specifically, the R can be C1-C20 alkyl substituted by one or more fluorines or C6-C50 aryl substituted by one or more fluorines.

[0057] In the step of forming an insulating film such as silicon oxide on the second region where no or relatively few shielding films are formed, methods such as sputtering, chemical vapor deposition (CVD, Chemical Vapor Deposition), or atomic layer deposition (ALD, Atomic Layer Deposition) can be used. Specifically, in the step of forming the insulating film, one or more selected from the group consisting of oxygen, hydrogen peroxide, ozone, nitric oxide, water plasma, oxygen plasma, residual water or oxygen in the chamber can be used as the oxygen supply source, and one or more selected from the group consisting of ammonia, hydrazine, alkyl hydrazine, dialkyl hydrazine, nitrogen plasma, nitrogen-hydrogen mixed gas plasma, ammonia plasma, ammonia-hydrogen mixed gas plasma, and mixtures thereof can be used as the nitrogen supply source.

[0058] Specifically, taking the silicon oxide insulating film as an example, the insulating film can be formed by repeating the four-step unit process of supplying the first raw material (Si precursor) - purging - supplying the second raw material (reactant) - purging, which is the same as the general atomic layer deposition (ALD) step. In addition, the insulating film formation process can be repeated multiple times until a film with a specific thickness is formed.

[0059] In addition, when repeating the insulating film formation process multiple times, the step of selectively forming a shielding film as described above can be additionally performed between each round in order to increase the selectivity ratio.

[0060] When a Si precursor is used as the first raw material, examples of the Si precursor may be silanes. Specifically, the silanes may be selected from SiH4, Diisoprophylamino Silane (DIPAS), Bis-Diethylamino Silane (BDEAS), Tris(dimethylamino)silane (TDMAS), Bis(t-butylamino)silane (BTBAS), or a combination thereof. The reactant used as the second raw material may be the oxygen supply source and the nitrogen supply source exemplified above.

[0061] In the insulating film forming process, an inert gas can be used for purging, and the inert gas used in the step of selectively forming the shielding film can also be used.

[0062] When performing the insulating film forming process, the shielding film can be removed by an oxidizing reactant or the like during the process, or all or part of it can remain.

[0063] As described above, after selectively forming an insulating film on the second region where no shielding film is formed or where a relatively small amount of shielding film is formed, an upper part of the insulating film is etched.

[0064] During the formation of the insulating film, the shielding film may be damaged by an oxidizing reactant, so a small amount of insulating film may also be deposited in the first region where the shielding film is formed. It is possible to etch only the insulating film formed in the first region using a mask, but this causes many inconveniences such as the need to fabricate a separate mask and align the mask to the pattern. Therefore, the upper part of the insulating film formed on the second region can be etched by performing an etching process to the extent that the insulating film formed in the first region can be removed. At this time, the shielding film that may remain in the first region may also be etched together.

[0065] As the etching method, various methods such as dry etching and wet etching can be used. Specifically, as dry etching, gas-phase etching using reactive gases such as NF3 and HF and plasma etching using plasmas such as hydrogen plasma and argon plasma can be employed. As wet etching, reactive solutions such as hydrofluoric acid and phosphoric acid can be used. In the case of wet etching, a washing process using deionized water can be performed subsequently to remove the solution remaining on the substrate surface.

[0066] At the same time, as Figure 2As shown, the steps of selectively forming a shielding film, the steps of selectively forming an insulating film, and the step of performing etching may be performed only once or repeatedly performed multiple times. The number of repetitions is not limited and may be repeatedly performed until the required thickness of the selective insulating film pattern of the semiconductor element is reached. As will be described in the subsequent embodiments, the selectivity can be improved through repeated processes, and the aspect ratio of the insulating film pattern can be significantly improved.

[0067] Meanwhile, an embodiment of the present invention provides a semiconductor element, 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 includes a first region selectively formed with a tin oxide insulating film and a second region where no or relatively less silicon oxide insulating film is formed, and the thickness difference of the silicon oxide insulating film formed on the first region and the second region is 4.5 nm or more, specifically 8.0 nm or more.

[0068] Among them, the same components and structures are the same as the above content, so they can be directly used. In the semiconductor element according to an embodiment of the present invention, a silicon oxide insulating film is selectively formed in two or more types of dielectric film regions, and the thickness difference of the insulating film is 4.5 nm or more. Therefore, a highly selective insulating film pattern can be achieved without using a separate mask pattern. In particular, the thickness difference of the insulating film can be increased to 8.0 nm or more by repeatedly performing multiple rounds of processes.

[0069] Next, the present invention will be described in more detail with reference to specific embodiments. The following embodiments are only illustrative of the present invention, and the scope of the present invention is not limited to the following embodiments.

[0070] <Test Example 1> Shielding Film Formation Method

[0071] In this test example, a shielding film was formed by introducing atomic layer deposition in a moving manner. The precursor for forming the shielding film was used in a tank, and the temperature of the tank was maintained at a specific temperature of -20 to 100 °C for stable supply.

[0072] One cycle of [precursor injection - purge for forming a shielding film] was carried out in the atomic layer deposition (ALD) process, and high-purity nitrogen (300 sccm) was used as the purge gas. It was repeated 1 to 100 times as needed. As the substrates, Si3N4 and SiO2 wafers were respectively treated with an HF aqueous solution or the treatment was omitted as used. The temperature of the substrates was adjusted to between 25 and 300 °C for the experiment. The results of the shielding film formation were confirmed using a water contact angle analysis device, and the results are shown in Table 1 below.

[0073] [Table 1]

[0074]

[0075] As shown in Table 1 above, it can be confirmed that when the shielding film is formed in the manner shown 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), and the contact angle difference is significantly larger compared to that of Comparative Example 1 without forming a shielding film, which is 3.1 degrees (Deg). In addition, it can be confirmed that in Comparative Example 1 with 1 aldehyde group, the number of carbon atoms in the alkyl group of 10 or more and no fluorine substituent, the contact angle difference is 6.5 degrees (Deg), and the contact angle difference is relatively small.

[0076] In addition, it can be confirmed that by pretreating the substrate, the contact angle difference is 22 degrees (Deg) or more, specifically in the range of 22 to 40 degrees (Deg), and the contact angle difference will increase significantly compared to the case without pretreatment.

[0077] <Test Example 2> Formation of a silicon oxide insulating film

[0078] In this test example, atomic layer deposition in a moving mode was introduced, and di-isopropylamino silane (DIPAS) was used as the Si precursor and ozone (O3) was used as the reactants for SiO2 film formation evaluation. The Si precursor was used in a can and was carried out without separate heating.

[0079] Atomic layer deposition (ALD) process was performed for 1 cycle in the sequence of [Si precursor injection - purge - reactant injection - purge], and high-purity nitrogen was used as the purge gas. It was repeated 1 to 200 cycles until a certain thickness was reached, and a capping film deposition process could be added between the processes. Si3N4 and SiO2 wafers with a capping film formed as in Test Example 1 were used as the substrates. Experiments were carried out with the substrate temperature 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.

[0080] [Table 2]

[0081]

[0082] As shown in Table 2, it can be confirmed that when the capping film is formed in the manner shown in Examples 8 to 14, the difference in the thickness of the insulating film is 0.8 nm or more, specifically in the range of 0.8 nm to 1.5 nm. Compared with the difference in the thickness of the insulating film in Comparative Example 3 without a capping film, which is 0.3 nm, the difference in the thickness of the insulating film is significantly larger. In addition, it can be confirmed that in Comparative Example 4 where there is 1 aldehyde group, the number of carbon atoms in the alkyl group is 10 or more and there is no fluorine substituent, the difference in the thickness of the insulating film is 0.7 nm, and the difference in the thickness of the insulating film is relatively small.

[0083] In addition, it can be confirmed that by pretreating the substrate, compared with the case without pretreatment, the difference in the thickness of the insulating film is 2.2 nm or more, specifically in the range of 2.8 nm to 5.0 nm, and the difference in the thickness of the insulating film will increase significantly.

[0084] <Test Example 3> Selective deposition method of the insulating film using a capping film formation - insulating film deposition - etching process

[0085] Using the same capping film formation method as in Test Example 1, a capping film was selectively formed after pretreating the substrate with an HF aqueous solution. Next, using the same silicon oxide insulating film formation method as in Test Example 2, the insulating film was formed with the number of cycles of the insulating film formation process halved.

[0086] Next, an etching process was performed using a low-concentration hydrofluoric acid. When etching with the low-concentration hydrofluoric acid, a wet etching process using an aqueous hydrofluoric acid solution was carried out, and after etching, deionized water (DI water) was used to remove the hydrofluoric acid solution and wash the surface. The concentration of the aqueous hydrofluoric acid solution was 0.1 Vol%, the etching was carried out for 7 seconds, and the surface washing with deionized water was carried out for 3 seconds. Etching was performed until the SiO2 insulating film deposited on the region where the shielding film was formed was completely removed. The presence or absence of the remaining insulating film was confirmed by the thickness of the SiO2 insulating film, and the film thickness was measured using an ellipsometer.

[0087] The three processes of the above-described shielding film deposition - insulating film deposition - etching process were carried out in sequence, and the process of sequentially completing the corresponding three processes was regarded as one round of the process. In the test example, a total of 6 rounds of the process were repeated. Table 3 shows the results of the film thickness measured using an ellipsometer.

[0088] [Table 3]

[0089]

[0090]

[0091]

[0092] As shown in Table 3 above, it can be confirmed that in the case of forming a shielding film and additionally performing an etching process, when the number of repeated rounds of the process increases, 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, so that ultra-fine patterns can be achieved with a high aspect ratio.

Claims

1. A method for forming an insulating film pattern, wherein, Comprising: The step of providing a substrate including two or more different types of dielectric film regions; The step of selectively forming a shielding film on the substrate, including a first region where a shielding film is formed and a second region where no shielding film or a relatively small amount of shielding film is formed; The step of selectively forming an insulating film on the second region; And The step of etching an upper part of the insulating film.

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

3. The method for forming an insulating film pattern according to claim 1, wherein After the step of forming the shielding film, the difference in the water contact angle between the first region and the second region is within the range of 7 to 50 degrees.

4. The method for forming an insulating film pattern according to claim 1, wherein Before the step of selectively forming the shielding film, a step of pre-treating the substrate is further included.

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

6. The method for forming an insulating film pattern according to claim 3, wherein In the step of performing the pre-treatment, it is carried out by impregnation in an HF aqueous solution or thermal annealing in an HF gas environment.

7. The method for forming an insulating film pattern according to claim 3, wherein In the step of performing the pre-treatment, it is carried out by thermal annealing or plasma treatment in an environment of N2, H2, ammonia, hydrazine or a mixed gas thereof.

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

9. 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 method for forming an insulating film pattern according to claim 1, wherein In the step of forming the insulating film, a sputtering, chemical vapor deposition or atomic layer deposition method is used.

11. The method for forming an insulating film pattern according to claim 2, wherein The precursor used when forming the silicon oxide insulating film is selected from SiH4, diisopropylaminosilane, bis(dimethylamino)silane, tris(dimethylamino)silane, bis(tert-butylamino)silane or a combination thereof.

12. The method for forming an insulating film pattern according to claim 1, wherein In the step of performing the etching, the insulating film formed in the first region is etched together.

13. The method for forming an insulating film pattern according to claim 12, wherein In the step of performing the etching, the shielding film formed in the first region is etched together.

14. The method for forming an insulating film pattern according to claim 1, wherein The step of selectively forming the shielding film, the step of selectively forming the insulating film, and the step of performing the etching are only performed once or repeated multiple times.

15. The method for forming an insulating film pattern according to claim 1, wherein, The precursor for forming the shielding film used in the step of selectively forming the shielding film is represented by the following Chemical Formula 1 or Chemical Formula 2: [Chemical Formula 1] [Chemical Formula 2] In 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 thioether group, or a substituted or unsubstituted C1-C30 or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C7-C50 aralkyl group, or a substituted or unsubstituted C2-C50 heteroaryl group, wherein, when the alkyl group has 10 or more carbon atoms, it is an alkyl group in which one or more hydrogens are substituted by halogen; and L is a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C1-C30 alkoxylene group, or a substituted or unsubstituted C1-C30 thioether 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. The method for forming an insulating film pattern according to claim 15, wherein, As the substituent, one or more are selected from the group consisting of deuterium, halogen, amino, cyano, nitrile, nitro, nitroso, aminosulfonyl, isothiocyanate, thiocyanate, carboxyl, C1-C30 alkyl, C1-C30 alkylsulfinyl, C1-C30 alkylsulfonyl, C1-C30 alkylsulfonate, C1-C12 fluoroalkyl, C2-C30 alkenyl, C1-C30 alkoxy, C1-C12 N-alkylamino, C2-C20 N,N-dialkylamino, C1-C30 thioether, C1-C6 N-alkylaminosulfonyl, C2-C12 N,N-dialkylaminosulfonyl, C3-C30 silyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C50 aryl, and heteroaryl, etc.

17. A semiconductor device, Wherein, Comprising: A substrate comprising two or more different 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 where a tin oxide insulating film is selectively formed and a second region where no or relatively less silicon oxide insulating film is formed, and the thickness difference of the silicon oxide insulating film formed on the first region and the second region is 4.5 nm or more.

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

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