Shielding compound, thin film forming method using the same, semiconductor substrate and semiconductor device manufactured therefrom

Abstract

The present invention relates to a shielding compound, a method for forming a thin film using the same, and a semiconductor substrate and a semiconductor device manufactured therefrom. A compound having a predetermined structure is provided as a shielding agent, and a deposition layer of uniform thickness is formed on a substrate as a shielding region according to the difference in the adsorption distribution pattern of the shielding agent, thereby reducing the deposition rate of the thin film, appropriately lowering the thin film growth rate, and significantly improving step coverage and thin film thickness uniformity even when a thin film is formed on a substrate having a complex structure, and reducing impurities.

Description

[Technical field]

[0001] The present invention relates to a shielding compound, a method for forming a thin film using the same, and a semiconductor substrate and a semiconductor device manufactured therefrom. More particularly, the present invention relates to a shielding compound that provides a compound having a predetermined structure as a shielding agent, and forms a deposition layer of uniform thickness on a substrate as a shielding region according to the difference in the adsorption distribution pattern of the shielding agent, thereby reducing the deposition rate of the thin film, appropriately lowering the thin film growth rate, and significantly improving step coverage and thin film thickness uniformity even when a thin film is formed on a substrate having a complex structure, and significantly reducing impurities, a method for forming a thin film using the same, and a semiconductor substrate and a semiconductor device manufactured therefrom. [Background technology]

[0002] Due to the increasing integration density of memory and non-memory semiconductor devices, the topography of substrates becomes more and more complex.

[0003] For example, the width and depth of the microstructure (hereinafter referred to as the "aspect ratio") is increasing to 20:1 or more, even 100:1 or more, and the larger the aspect ratio, the more difficult it becomes to form a deposition layer of uniform thickness along the complex microstructure surface.

[0004] As a result, step coverage, which defines the thickness ratio of the deposition layer formed on the top and bottom of the microstructure in the depth direction, is reaching a level of 90%, making it increasingly difficult for devices to exhibit electrical characteristics, and so its importance is increasing. Since 100% step coverage means that the thickness of the deposition layer formed on the top and bottom of the microstructure is the same, technological development is needed to get the step coverage as close to 100% as possible.

[0005] The semiconductor thin film is made of a nitride film, an oxide film, a metal film, etc. Examples of the nitride film include silicon nitride (SiN), titanium nitride (TiN), and tantalum nitride (TaN), and examples of the oxide film include silicon oxide (SiO 2), hafnium oxide (HfO 2 ), zirconium oxide (ZrO 2 ), and the metal film includes a film of molybdenum (Mo), tungsten (W), and the like.

[0006] The thin film is generally used as a diffusion barrier between the silicon layer of a doped semiconductor and aluminum (Al), copper (Cu), etc., which are used as interlayer wiring materials, but is also used as an adhesion layer when a tungsten (W) thin film is deposited on a substrate.

[0007] Meanwhile, as discussed above, in order for the thin film deposited on the substrate to have excellent and uniform physical properties, high step coverage of the thin film is essential, so the ALD (atomic layer deposition) process, which utilizes surface reactions, is used rather than the CVD (chemical vapor deposition) process, which mainly utilizes gas phase reactions. However, there are still problems in achieving 100% step coverage.

[0008] When the deposition temperature is increased in order to achieve 100% step coverage, step coverage becomes difficult. First, in a deposition process consisting of two types of precursor and reactant, an increase in deposition temperature not only leads to a steep increase in the growth rate of thin films (GPC), but even if an ALD process is performed at 300°C to mitigate the increase in GPC caused by an increase in deposition temperature, the deposition temperature increases during the process, making it difficult to say that it is a solution.

[0009] Therefore, methods have been proposed to slow down the thin film growth rate, but when the deposition temperature is reduced to slow down the thin film growth rate, the amount of remaining impurities such as carbon and chlorine in the thin film increases, resulting in a significant deterioration of the film quality (see paper J. Vac. Sci. Technol. A, 35(2017) 01B130).

[0010] According to the above-mentioned document, it was confirmed that process by-products such as chlorides remain in the manufactured thin film, which induces corrosion of metals such as aluminum, and that the generation of non-volatile by-products leads to deterioration of the film quality.

[0011] Therefore, there is a need to develop a method for forming a thin film that allows the formation of thin films with complex structures, has a low amount of residual impurities, and greatly improves step coverage and thickness uniformity of the thin film, as well as semiconductor substrates and semiconductor devices manufactured using the method. Summary of the Invention [Problem to be solved by the invention]

[0012] In order to solve the above-mentioned problems of the prior art, the present invention aims to provide a shielding compound that forms a deposition layer of uniform thickness on a substrate as a shielding region for a thin film according to the difference in the adsorption distribution pattern of a predetermined shielding agent, thereby reducing the deposition rate of the thin film and appropriately lowering the thin film growth rate, thereby significantly improving step coverage and thin film thickness uniformity even when a thin film is formed on a substrate having a complex structure, a thin film formation method using the same, and a semiconductor substrate and a semiconductor device manufactured therefrom.

[0013] An object of the present invention is to improve the density, electrical properties, and dielectric properties of a thin film by improving the crystallinity and oxidation fraction of the thin film.

[0014] The above and other objects of the present invention can all be achieved by the present invention described below. [Means for solving the problem]

[0015] In order to achieve the above object, the present invention provides a thin film shielding compound comprising a linear or cyclic saturated or unsaturated hydrocarbon having two or more of nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) and having 3 to 15 carbon atoms.

[0016] The thin film shielding compound may have a structure containing nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) at either end of a central carbon atom connected to oxygen by a double bond.

[0017] The thin film shielding compound may have a structure containing nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) at one end of a central carbon atom connected to oxygen by a double bond and carbon (C) at the other end.

[0018] The thin film shielding compound may be at least one selected from the group consisting of compounds represented by the following Formula 1 and Formula 2:

[0019] [Chemical formula 1]

[0020] [ka]

[0021] [Chemical formula 2]

[0022] [ka]

[0023] (A is oxygen (O), sulfur (S), phosphorus (P), nitrogen (N), -CH, or -CH 2 and

[0024] The B is -OH, -OCH 3 , -OCH 2 CH 3 , -CH 2 CH 3 , -SH, -SCH 3 , or -SCH 2 CH 3 and

[0025] wherein R' and R'' are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

[0026] The n is an integer from 0 to 3.

[0027] The shielding compound may have a deposition rate reduction rate, expressed by the following formula 1, of 30% or more.

[0028] [Formula 1]

[0029]

number

[0030] (In the above formula, DRn is a depth rate measured for a thin film prepared without adding the shielding compound, and DRw is a depth rate measured for a thin film prepared with adding the shielding compound, where the depth rate is a value measured for a thin film having a thickness of 3 to 30 nm at room temperature and pressure using an ellipsometer device, and is expressed in Å / cycle units.)

[0031] The shielding compound may have a refractive index of less than or equal to 1.39, 1.41 to 1.42, 1.43 to 1.44, or 1.45 to 1.46.

[0032] The shielding compound may be one or more selected from compounds represented by the following formulas 1-1 to 1-4 and 2-1 to 2-4.

[0033] [Chemical Formula 1-1 to 1-4]

[0034] [ka]

[0035] [Chemical Formula 2-1 to 2-4]

[0036] [ka]

[0037] The shielding compound may provide a shielding region for an oxide film, a nitride film, a metal film, or selective thin films thereof.

[0038] The shielding region may be formed on the entire substrate or a portion of the substrate on which the oxide film, nitride film, metal film, or a selective thin film thereof is formed.

[0039] When the total area of ​​the entire substrate or the part of the substrate is taken as 100%, the shielded area may occupy 10 to 95% of the total area, and the unshielded area may occupy the remaining area.

[0040] When the total area of ​​the entire substrate or a portion of the substrate is taken as 100%, the first shielded region may occupy 10 to 95% of the total area, the second shielded region may occupy 10 to 95% of the remaining area, and the remaining area may be an unshielded region.

[0041] The thin film may be a laminated film of one or more elements selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd.

[0042] The thin film may be used as a diffusion barrier film, an etching stop film, an electrode film, a dielectric film, a gate insulating film, a block oxide film, or a charge trap.

[0043]

[0044] The present invention also provides a method for forming a thin film, comprising the step of injecting a shielding compound having a structure represented by the following Formula 1 or Formula 2 into a chamber to shield a surface of a loaded substrate:

[0045] [Chemical formula 1]

[0046] [ka]

[0047] [Chemical formula 2]

[0048] [ka]

[0049] (A is oxygen (O), sulfur (S), phosphorus (P), nitrogen (N), -CH, or -CH 2 and

[0050] The B is -OH, -OCH 3 , -OCH 2 CH 3 , -CH 2 CH 3 , -SH, -SCH 3 , or -SCH 2 CH 3 and

[0051] R' and R'' are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and n is an integer of 0 to 3.

[0052]

[0053] The present invention also provides a method for producing a semiconductor device comprising the steps of:

[0054] i) vaporizing the shielding compound to form a shielding region on a surface of a substrate loaded in a chamber;

[0055] ii) initially purging the interior of the chamber with a purge gas;

[0056] iii) vaporizing a precursor compound and adsorbing it in the area outside the shielded area;

[0057] iv) second purging the interior of the chamber with a purge gas;

[0058] v) supplying a reaction gas into the chamber; and

[0059] vi) tertiary purging of the inside of the chamber with a purge gas.

[0060]

[0061] The present invention also provides a method for producing a semiconductor device comprising the steps of:

[0062] i) vaporizing a precursor compound and adsorbing it onto a substrate surface loaded in a chamber;

[0063] ii) initially purging the interior of the chamber with a purge gas;

[0064] iii) vaporizing the shielding compound to shield a substrate surface loaded in the chamber;

[0065] iv) second purging the interior of the chamber with a purge gas;

[0066] v) supplying a reaction gas into the chamber; and

[0067] vi) tertiary purging of the inside of the chamber with a purge gas.

[0068] The precursor compound may be a molecule composed of one or more selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd, and may be a precursor having a vapor pressure of more than 0.01 mTorr and not more than 100 Torr at 25°C.

[0069] The chamber may be an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0070] The shielding compound or precursor compound may be vaporized and injected, followed by a plasma post-treatment step.

[0071] The amount of the purge gas introduced into the chamber in each of the steps ii) and iv) may be 10 to 100,000 times the volume of the introduced shielding compound.

[0072] The reaction gas may be a nitriding agent, an oxidizing agent, or a reducing agent, and the reaction gas, the shielding compound, and the precursor compound may be delivered into the chamber by a VFC method, a DLI method, or an LDS method.

[0073] The thin film may be a silicon nitride film, a silicon oxide film, a titanium nitride film, a titanium oxide film, a tungsten nitride film, a molybdenum nitride film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, or an aluminum oxide film.

[0074] The substrate loaded in the chamber may be heated at 100 to 800° C., and the input amount (mg / cycle) ratio of the shielding compound to the precursor compound in the chamber may be 1:1 to 1:20.

[0075]

[0076] The present invention also provides a semiconductor substrate which is manufactured by the above-mentioned thin film forming method.

[0077] The thin film may have a multi-layer structure of two or three layers.

[0078]

[0079] The present invention also provides a semiconductor device including the semiconductor substrate described above.

[0080] The semiconductor substrate may be low resistive metal gate interconnects, high aspect ratio 3D metal-insulator-metal (MIM) capacitors, DRAM trench capacitors, 3D Gate-All-Around (GAA), or 3D NAND flash memory. Effect of the Invention

[0081] According to the present invention, there is an effect of providing a shielding compound that reduces the deposition rate of a thin film by forming a shielding region for the thin film on a substrate, and appropriately reduces the thin film growth rate, thereby improving step coverage even when a thin film is formed on a substrate having a complex structure.

[0082] In addition, the by-products produced during the thin film formation process are more effectively reduced, corrosion and deterioration are prevented, and the crystallinity of the thin film is improved, thereby improving the electrical properties of the thin film.

[0083] In addition, the amount of process by-products during thin film formation can be reduced, and step coverage and thin film density can be improved, thereby providing a thin film formation method using the same, and a semiconductor substrate and a semiconductor device manufactured using the same. [Brief description of the drawings]

[0084] [Figure 1] FIG. 1 is a SIMS analysis graph of the HfO2 thin film produced in Example 4.

[0085] [Diagram 2] FIG. 2 is a SIMS analysis graph of the HfO2 thin film produced in Comparative Example 4.

[0086] [Diagram 3] FIG. 3 is a graph showing the ratio of hafnium (Hf) to oxygen (O) in the thin film produced in Comparative Example 3.

[0087] [Figure 4] FIG. 4 is a graph showing the ratio of hafnium (Hf) to oxygen (O) in the thin film produced in Example 8.

[0088] [Diagram 5] FIG. 5 shows TEM images of test pieces cut horizontally at a position 100 nm below the top (left drawing) and at a position 100 nm above the bottom (right drawing) of a thin film deposited under the conditions of Example 4 on a substrate with a complex structure and an aspect ratio of 22:1.

[0089] [Figure 6] FIG. 6 shows TEM images of test pieces cut horizontally at a position 100 nm below the top (left drawing) and at a position 100 nm above the bottom (right drawing) of a thin film deposited under the conditions of Example 5 on a substrate with a complex structure and an aspect ratio of 22:1.

[0090] [Figure 7] FIG. 7 is a drawing showing the XRD crystal patterns of Comparative Example 4 (black) and Example 1 (blue). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0091] The presently described shielding compound, a method for forming a thin film using the same, and a semiconductor substrate and a semiconductor device manufactured therefrom will now be described in detail.

[0092] In this description, unless otherwise specified, the term "shielding" means not only reducing, preventing or blocking precursor compounds for forming a thin film from being adsorbed onto a substrate, but also reducing, preventing or blocking process by-products from being adsorbed onto a substrate.

[0093] The present inventors have confirmed that a shielding compound that shields a precursor compound for forming a thin film on a substrate surface loaded into a chamber, which provides a compound with a predetermined structure as a shielding agent, forms a uniformly thick deposition layer due to the difference in the adsorption distribution map of the shielding agent as a shielding region that does not remain in the thin film, and forms a relatively sparse thin film, and at the same time, the growth rate of the formed thin film is significantly reduced, so that even when applied to a substrate with a complex structure, the uniformity of the thin film is ensured and the step coverage is greatly improved, and in particular, it is possible to deposit it at a thin thickness, and even the amount of O, Si, metal, metal oxide, and carbon residues that were left as process by-products, which were difficult to reduce in the past, are improved. Based on this, the present invention has been completed by conducting research into a shielding compound that provides a shielding region.

[0094]

[0095] The shielding compounds of the present invention provide thin film shielding compounds.

[0096] The thin film may be provided as one or more precursors selected from the group consisting of, for example, Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd, and may provide an oxide film, a nitride film, a metal film, or a shielding region for a selective thin film thereof. In this case, the effect to be achieved in the present invention can be sufficiently obtained.

[0097] Specific examples of the thin film include a silicon nitride film, a silicon oxide film, a titanium nitride film, a titanium oxide film, a tungsten nitride film, a molybdenum nitride film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, and an aluminum oxide film.

[0098] The thin film may include the above-mentioned film compositions alone or in selective areas, but is not limited thereto, and may also include SiH and SiOH.

[0099] The thin film may be used in semiconductor devices not only as a commonly used diffusion barrier film, but also as an etching stop film, an electrode film, a dielectric film, a gate insulating film, a block oxide film, or a charge trap.

[0100]

[0101] The shielding compound is characterized by containing linear or cyclic saturated or unsaturated hydrocarbons having two or more types of nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) and having 3 to 15 carbon atoms. In this case, when a thin film is formed, a shielding region that does not remain in the thin film is formed to form a relatively sparse thin film, and at the same time, side reactions are suppressed to control the thin film growth rate, process by-products in the thin film are reduced to reduce corrosion and deterioration, the crystallinity of the thin film is improved, a stoichiometric oxidation state is reached when a metal oxide film is formed, and step coverage and thickness uniformity of the thin film are greatly improved even when a thin film is formed on a substrate having a complex structure.

[0102] As a specific example, the shielding compound has a structure containing nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) at both ends of a central carbon atom connected to oxygen through a double bond, thereby achieving a large reduction in process by-products, excellent step coverage, improved thin film density and excellent thin film electrical properties.

[0103] Here, the structure containing nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) at both ends of the central carbon atom connected to the oxygen by a double bond as described above refers to the following unless otherwise specified. [ka]

[0104] As a specific example, the shielding compound has a structure containing nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) at one end of a central carbon atom connected to oxygen through a double bond and carbon (C) at the other end, which can provide a large reduction in process by-products, excellent step coverage, improved thin film density, and superior thin film electrical properties.

[0105] Here, the structure containing nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) at one end of the central carbon atom connected to the above-mentioned oxygen by a double bond and carbon (C) at the other end refers to the following, unless otherwise specified. [ka]

[0106]

[0107] Specific examples of the shielding compound include at least one selected from the group consisting of the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2. In this case, a shielding region that does not remain in the thin film during thin film formation is formed to form a relatively sparse thin film, while at the same time, side reactions are suppressed to control the thin film growth rate, process by-products in the thin film are reduced to reduce corrosion and deterioration, the crystallinity of the thin film is improved, and even when a thin film is formed on a substrate having a complex structure, step coverage and thickness uniformity of the thin film can be significantly improved.

[0108] [Chemical formula 1]

[0109] [ka]

[0110] [Chemical formula 2]

[0111] [ka]

[0112] (A is oxygen (O), sulfur (S), phosphorus (P), nitrogen (N), -CH, or -CH 2 and

[0113] The B is -OH, -OCH 3 , -OCH 2 CH 3 , -CH 2 CH 3 , -SH, -SCH 3 , or -SCH 2 CH 3 and

[0114] R' and R'' are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

[0115] The n is an integer from 0 to 3.

[0116] In the above Chemical Formula 1, A is oxygen (O) or sulfur (S), and preferably oxygen (O). In this case, there are advantages in that the effect of reducing process by-products is large, the step coverage is excellent, the effect of improving the thin film density, and the electrical properties, insulating properties and dielectric properties of the thin film are excellent.

[0117] The R' is an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms. In this case, there are advantages in that the effect of reducing process by-products is large, the step coverage is excellent, the effect of improving the thin film density, and the electrical properties, insulating properties, and dielectric properties of the thin film are excellent.

[0118] The above n is an integer of 1 or 2, and is preferably an integer of 1.

[0119] In the above formula 2, B is -OH, -OCH 3 , -OCH 2 CH 3 , -CH 2 CH 3 , -SH, -SCH 3 , or -SCH 2 CH 3In this case, there are advantages in that the amount of process by-products is greatly reduced, the step coverage is excellent, the thin film density is improved, and the electrical properties of the thin film are excellent.

[0120] The R″ is an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms. In this case, there are advantages in that the effect of reducing process by-products is large, the step coverage is excellent, the effect of improving the thin film density, and the electrical properties of the thin film are excellent.

[0121] When the compounds represented by Formula 1 or 2 have a saturated structure, the efficiency of the deposition process can be increased.

[0122] The compounds represented by Formula 1 and Formula 2 may exclude structures containing halogen.

[0123]

[0124] The shielding compound, preferably the compound represented by Formula 1 or Formula 2, may have a deposition rate reduction rate of 30% or more, specifically 35% or more, preferably 38% or more, as represented by Formula 1 below. In this case, a deposition layer of uniform thickness due to the difference in the adsorption distribution of the shielding agent having the above-mentioned structure is formed as a shielding region that does not remain in the thin film, forming a relatively sparse thin film, and at the same time, the growth rate of the formed thin film is significantly reduced, so that even when applied to a substrate with a complex structure, the uniformity of the thin film is ensured and the step coverage is greatly improved, and in particular, deposition can be performed at a thin thickness, and the amount of O, Si, metal, metal oxide, and even carbon remaining as process by-products, which was previously difficult to reduce, can be improved.

[0125] [Formula 1]

[0126]

number

[0127] (In the above formula, DRn is a depth rate measured for a thin film prepared without adding the shielding compound, and DRw is a depth rate measured for a thin film prepared with adding the shielding compound, where the depth rate is a value measured for a thin film having a thickness of 3 to 30 nm under normal temperature and pressure conditions using an ellipsometer device, and is expressed in Å / cycle units.)

[0128] In Equation 1, the thin film growth rate per cycle when a shielding compound is used and when a shielding compound is not used means the thin film deposition thickness (Å / cycle) per cycle, i.e., the deposition rate. For example, the deposition rate can be calculated by measuring the final thickness of a thin film having a thickness of 3 to 30 nm using an ellipsometer under room temperature and pressure conditions, and then dividing the measured thickness by the total number of cycles to obtain an average deposition rate.

[0129] In the above formula 1, "when no shielding compound was used" means that only a precursor compound is adsorbed onto a substrate in a thin film deposition process to produce a thin film. A specific example of the thin film formation method is that the step of adsorbing a shielding compound and the step of purging unadsorbed shielding compound are omitted to form a thin film.

[0130]

[0131] For example, in the case of a compound represented by Chemical Formula 1, the shielding compound may have a refractive index in the range of 1.4 to 1.42, or 1.43 to 1.5, specifically 1.41 to 1.417, or 1.43 to 1.47, preferably 1.413 to 1.417, or 1.450 to 1.452.

[0132] For example, the shielding compound may be a compound represented by Formula 2 having a refractive index of 1.39 or less, specifically 1.3 to 1.39, preferably 1.35 to 1.385.

[0133] In this case, a uniformly thick deposition layer is formed on the substrate due to the difference in the adsorption distribution of the blocking agent having the above-mentioned structure, and a blocking region is formed that does not remain in the thin film, thereby reducing the deposition rate of the thin film, and even when a thin film is formed on a substrate having a complex structure by appropriately lowering the thin film growth rate, step coverage and thin film thickness uniformity are greatly improved, and the adsorption of not only the thin film precursor but also the process by-products is prevented, thereby effectively protecting the surface of the substrate and effectively removing the process by-products.

[0134] In particular, since a relatively sparse thin film is formed and the growth rate of the formed thin film is significantly reduced, the uniformity of the thin film is ensured even when applied to a substrate with a complex structure, and the step coverage is greatly improved. In particular, it is possible to deposit a thin film, and it is possible to provide the effect of improving the amount of O, Si, metal, metal oxide, and even carbon residues that were previously difficult to reduce as process by-products.

[0135]

[0136] The compound represented by Chemical Formula 1 may be one or more selected from the compounds represented by Chemical Formulas 1-1 to 1-4 below. In this case, the compound has a high effect of providing a thin film shielding region to control the growth rate of the thin film, a high effect of removing process by-products, and an excellent effect of improving step coverage and film quality.

[0137] [Chemical Formula 1-1 to 1-4]

[0138] [ka]

[0139] The compound represented by Chemical Formula 2 may be one or more selected from the compounds represented by Chemical Formulas 2-1 to 2-4 below. In this case, the compound has a high effect of providing a thin film shielding region to control the growth rate of the thin film, a high effect of removing process by-products, and an excellent effect of improving step coverage and film quality.

[0140] [Chemical Formula 2-1 to 2-4]

[0141] [ka]

[0142] The shielding compound can provide a shielding region for a thin film.

[0143] For example, the thin film shielding region may be formed on the entire substrate or a portion of the substrate on which the thin film is formed.

[0144] Furthermore, when the total area of ​​the entire substrate or a portion of the substrate is taken as 100%, the shielding region for the thin film may occupy, for example, 10 to 95% of the area, specifically 15 to 90% of the area, preferably 20 to 85% of the area, more preferably 30 to 80% of the area, even more preferably 40 to 75% of the area, and even more preferably 40 to 70% of the area, and the unshielded region may occupy the remaining area.

[0145] Furthermore, when the total area of ​​the entire substrate or a portion of the substrate is taken as 100%, the first shielding region may occupy an area of ​​10 to 95%, for example, 15 to 90%, preferably 20 to 85%, more preferably 30 to 80%, even more preferably 40 to 75%, and even more preferably 40 to 70%, of the remaining area, and the second shielding region may occupy an area of ​​10 to 95%, for example, 15 to 90%, preferably 20 to 85%, more preferably 30 to 80%, even more preferably 40 to 75%, and even more preferably 40 to 70%, of the remaining area, and the remaining area may be an unshielded region.

[0146]

[0147] The thin film shielding region is characterized in that it does not remain on the thin film.

[0148] In this case, unless otherwise specified, not remaining refers to the presence of C element less than 0.1 atom %, Si element less than 0.1 atom %, N element less than 0.1 atom %, and halogen elements less than 0.1 atom % when analyzed by XPS. More preferably, in a secondary-ion mass spectrometry (SIMS) measurement method that measures by penetrating into the substrate in the depth direction, or an X-ray Photoelectron Spectroscopy (XPS) measurement method, considering the increase / decrease rate of C, N, Si, and halogen impurities before and after using a shielding agent under similar deposition conditions, it is preferable that the increase / decrease rate of the signal sensitivity (intensity) of each element type does not exceed 5%.

[0149] As an example, the thin film may contain a halogen compound at 100 ppm or less.

[0150] The thin film may be used as an etching stop layer, an electrode layer, a dielectric layer, a gate insulating layer, a block oxide layer, or a charge trap, but is not limited thereto.

[0151] The shielding compound may preferably be a compound with a purity of 99.9% or more, a compound with a purity of 99.95% or more, or a compound with a purity of 99.99% or more. For reference, when a compound with a purity of less than 99% is used, impurities may remain in the thin film or cause side reactions with the precursor or reactant, so it is preferable to use a substance with a purity of 99% or more.

[0152]

[0153] The shielding compound is preferably used in an atomic layer deposition (ALD) process, and in this case, it has the advantage that it does not interfere with the adsorption of precursor compounds, but effectively protects the substrate surface as a shielding compound, and effectively removes process by-products.

[0154] The shielding compound is preferably liquid at room temperature (22° C.) and has a density of 0.8 to 2.5 g / cm3 or 0.8 to 1.5 g / cm 3 The vapor pressure (20°C) may be 0.1 to 300 mmHg or 1 to 300 mmHg. Within this range, a shielding region is effectively formed, and there is an effect of excellent step coverage, thin film thickness uniformity, and film quality improvement.

[0155] More preferably, the shielding compound has a density of 0.75 to 2.0 g / cm 3 or 0.8 to 1.3 g / cm 3 The vapor pressure (20° C.) may be 1 to 260 mmHg. Within this range, a shielding region is effectively formed, and there is an effect of excellent step coverage, thin film thickness uniformity, and film quality improvement.

[0156]

[0157] The method for forming a thin film of the present invention is characterized by including a step of injecting a shielding compound represented by the following Formula 1 or Formula 2 into a chamber to shield a loaded substrate surface. In this case, a shielding region for the thin film is formed on the substrate to reduce the deposition rate of the thin film, and the thin film growth rate is appropriately reduced, which has the effect of significantly improving step coverage and thickness uniformity of the thin film even when a thin film is formed on a substrate having a complex structure.

[0158] [Chemical formula 1]

[0159] [ka]

[0160] [Chemical formula 2]

[0161] [ka]

[0162] (A is oxygen (O), sulfur (S), phosphorus (P), nitrogen (N), -CH, or -CH 2 and

[0163] The B is -OH, -OCH 3 , -OCH 2 CH 3 , -CH 2 CH 3 , -SH, -SCH 3 , or -SCH 2 CH 3 and

[0164] R' and R'' are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and n is an integer of 0 to 3.

[0165]

[0166] In the step of shielding the shielding compound on the substrate surface, the feeding time (sec) of the shielding compound on the substrate surface is preferably 0.01 to 5 seconds per cycle, more preferably 0.02 to 3 seconds, even more preferably 0.04 to 2 seconds, and even more preferably 0.05 to 1 second. Within this range, the thin film growth rate is low, and there are advantages in terms of excellent step coverage and cost-effectiveness.

[0167] In this description, the feeding time of the shielding compound is based on a flow rate of 0.1 to 50 mg / cycle with a chamber volume of 15 to 20 L, and more specifically, based on a flow rate of 0.8 to 20 mg / cycle with a chamber volume of 18 L.

[0168] In a preferred embodiment, the method for forming a thin film may include the steps of: i) vaporizing the shielding compound and shielding it on the surface of a substrate loaded in a chamber; ii) first purging the inside of the chamber with a purge gas; iii) vaporizing a precursor compound and adsorbing it on the surface of a substrate loaded in the chamber; iv) second purging the inside of the chamber with a purge gas; v) supplying a reaction gas into the chamber; and vi) third purging the inside of the chamber with a purge gas. In this case, the steps i) to vi) may be repeated as a unit cycle until a thin film of a desired thickness is obtained. In this way, when the shielding compound of the present invention is introduced before the precursor compound in one cycle and adsorbed on the substrate, there are advantages that the thin film growth rate can be appropriately reduced even when deposited at a high temperature, and the resistivity of the thin film is reduced by effectively removing the process by-products generated, and the step coverage is greatly improved.

[0169]

[0170] In another preferred embodiment, the method for forming a thin film may include the steps of: i) vaporizing a precursor compound and adsorbing it on the surface of a substrate loaded in a chamber; ii) first purging the inside of the chamber with a purge gas; iii) vaporizing the shielding compound and adsorbing it on the surface of a substrate loaded in the chamber; iv) second purging the inside of the chamber with a purge gas; v) supplying a reaction gas into the inside of the chamber; and vi) third purging the inside of the chamber with a purge gas. In this case, the steps i) to vi) may be regarded as a unit cycle, and the cycle may be repeated until a thin film of a desired thickness is obtained. In this way, when the shielding compound of the present invention is added after the precursor compound in one cycle and adsorbed on the substrate, the shielding compound can act as a growth activator for thin film formation, and in this case, there are advantages in that the thin film growth rate is increased, and the density and crystallinity of the thin film are increased, so that the resistivity of the thin film is reduced and the electrical properties are greatly improved.

[0171]

[0172] In a preferred embodiment of the method for forming a thin film of the present invention, the shielding compound of the present invention can be added prior to the precursor compound in one cycle to be adsorbed onto the substrate. In this case, even when the thin film is deposited at a high temperature, the thin film growth rate can be appropriately reduced, so that the process by-products can be significantly reduced and the step coverage can be significantly improved. The thin film can have an increased film forming property and a reduced thin film resistivity. Even when applied to a semiconductor device having a large aspect ratio, the thickness uniformity of the thin film can be significantly improved, ensuring the reliability of the semiconductor device.

[0173]

[0174] In the thin film formation method, for example, when the shielding compound is deposited before or after the deposition of the precursor compound, the unit cycle may be repeated 1 to 99,999 times as necessary, preferably 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times, and within this range, the desired thin film thickness can be obtained while the effects to be achieved in the present invention can be sufficiently obtained.

[0175]

[0176] The precursor compound is a molecule having one or more ligands consisting of C, N, O, and H with Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd as a central metal atom, and in the case of a precursor having a vapor pressure of 1 mTorr to 100 Torr at 25°C, the effect of forming a shielding region by the above-mentioned shielding compound can be maximized.

[0177] The precursor compound is not limited as long as it is a compound known in the art. For example, a compound containing a cyclopentadienyl group may be used. Specifically, an example of a hafnium precursor compound is CpHf(NMe 2 ) 3) tris(dimethylamido)cyclopentadienylhafnium and Cp(CH 2 ) 3 NM 3 Hf(NMe 2 ) 2 (Methyl-3-cyclopentadienylpropylamino)bis(dimethylamino)hafnium and the like may also be used.

[0178] In the present invention, the chamber may be, for example, an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0179] In the present invention, the shielding compound or precursor compound may be vaporized and then injected, followed by plasma post-treatment, which can improve the thin film growth rate and reduce process by-products.

[0180]

[0181] When the shielding compound is first adsorbed on the substrate and then the precursor compound is adsorbed, or when the shielding compound is first adsorbed on the substrate and then the precursor compound is adsorbed, the amount of purge gas introduced into the chamber in the step of purging the unadsorbed shielding compound is not particularly limited as long as it is sufficient to remove the unadsorbed shielding compound. For example, it may be 10 to 100,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times, and within this range, the unadsorbed shielding compound can be sufficiently removed to form a uniform thin film and prevent deterioration of the film quality. Here, the amounts of the purge gas and the shielding compound introduced are based on one cycle, and the volume of the shielding compound refers to the volume of vaporized shielding compound vapor.

[0182] As a specific example, when the shielding compound is injected (per cycle) at a flow rate of 1.66 mL / s and an injection time of 0.5 sec, and in the step of purging unadsorbed shielding compound, a purge gas is injected (per cycle) at a flow rate of 166.6 mL / s and an injection time of 3 sec, the amount of purge gas injected is 602 times the amount of shielding compound injected.

[0183]

[0184] In addition, the amount of purge gas introduced into the chamber in the step of purging the unadsorbed precursor compound is not particularly limited as long as it is sufficient to remove the unadsorbed precursor compound. For example, the amount may be 10 to 10,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times, based on the volume of the precursor compound introduced into the chamber, and within this range, the unadsorbed precursor compound can be sufficiently removed to form a uniform thin film and prevent deterioration of the film quality. Here, the amounts of the purge gas and the precursor compound introduced are each based on one cycle, and the volume of the precursor compound means the volume of the vaporized precursor compound vapor.

[0185]

[0186] In addition, the amount of purge gas introduced into the ALD chamber in the purging step performed immediately after the reaction gas supply step may be, for example, 10 to 10,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times the volume of the reaction gas introduced into the ALD chamber, and the desired effect can be sufficiently obtained within this range. Here, the amounts of the purge gas and the reaction gas introduced are each based on one cycle.

[0187]

[0188] The shielding compound and precursor compound may be delivered into the ALD chamber preferably by VFC, DLI or LDS, more preferably by LDS.

[0189] The substrate loaded in the chamber may be heated to, for example, 50 to 400° C., and the shielding compound or precursor compound may be injected onto the substrate in a heated or unheated state, or the heating conditions may be adjusted during the deposition process after being injected unheated according to deposition efficiency. For example, the shielding compound or precursor compound may be injected onto the substrate at 50 to 400° C. for 1 to 20 seconds.

[0190]

[0191] The ratio of the amount (mg / cycle) of the shielding compound to the precursor compound fed into the chamber may be preferably 1:1.5 to 1:20, more preferably 1:2 to 1:15, even more preferably 1:2 to 1:12, and even more preferably 1:2.5 to 1:10. Within this range, the effect of improving step coverage and the effect of reducing process by-products are large.

[0192]

[0193] In the present invention, the precursor compound may be mixed with a non-polar solvent and then introduced into the chamber. In this case, there is an advantage that the viscosity and vapor pressure of the precursor compound can be easily adjusted.

[0194] The non-polar solvent may be at least one selected from the group consisting of alkanes and cycloalkanes. In this case, the non-polar solvent has the advantage of improving step coverage even when the deposition temperature is increased during thin film formation, while containing an organic solvent having low reactivity and solubility and easy moisture management.

[0195] In a more preferred embodiment, the non-polar solvent is 1 Or C10 Alkanes of C 3 Or C 10 and preferably C 3 Or C 10 In this case, the reactivity and solubility are low, and water management is easy.

[0196] In this description, C 1 , C 3 etc. mean the number of carbon atoms.

[0197] The cycloalkane is preferably 3 Or C 10 Among the monocycloalkanes, cyclopentane is preferred in the vapor deposition process because it is liquid at room temperature and has the highest vapor pressure, but is not limited thereto.

[0198] The non-polar solvent has, for example, a solubility in water (25° C.) of 200 mg / L or less, preferably 50 to 400 mg / L, and more preferably 135 to 175 mg / L. Within this range, the non-polar solvent has the advantages of low reactivity with the precursor compound and easy moisture management.

[0199] The solubility in this description is not particularly limited as long as it is based on a measurement method or standard commonly used in the technical field to which the present invention pertains. For example, a saturated solution may be measured by HPLC.

[0200] The non-polar solvent may preferably be contained in an amount of 5 to 95% by weight, more preferably 10 to 90% by weight, even more preferably 40 to 90% by weight, and most preferably 70 to 90% by weight, based on the total weight of the precursor compound and the non-polar solvent.

[0201] If the content of the non-polar solvent exceeds the upper limit, impurities are generated, and the number of impurities in the resistor and thin film increases. If the content of the organic solvent is less than the lower limit, the effect of improving step coverage and the effect of reducing impurities such as chlorine (Cl) ions by adding the solvent are not so good.

[0202]

[0203] In the thin film forming method, when the shielding compound, preferably the compound represented by Formula 1 or Formula 2, is used, the deposition rate reduction rate represented by Formula 1 may be 30% or more, specifically 35% or more, preferably 38% or more. In this case, a deposition layer of uniform thickness due to the difference in the adsorption distribution of the shielding agent having the above structure is formed as a shielding region that does not remain in the thin film, forming a relatively sparse thin film. At the same time, the growth rate of the thin film formed is significantly reduced, so that the uniformity of the thin film is ensured even when applied to a substrate with a complex structure, and the step coverage is greatly improved. In particular, deposition can be performed at a thin thickness, and the amount of O, Si, metal, metal oxide, and even carbon remaining as process by-products, which was difficult to reduce in the past, can be improved.

[0204] [Formula 1]

[0205]

number

[0206] (In the above formula, DRn is a depth rate measured for a thin film prepared without adding the shielding compound, and DRw is a depth rate measured for a thin film prepared with adding the shielding compound, where the depth rate is a value measured for a thin film having a thickness of 3 to 30 nm under normal temperature and pressure conditions using an ellipsometer device, and is expressed in Å / cycle units.)

[0207] In the thin film formation method, the residual halogen intensity (c / s) in the thin film at 100°C, as measured based on SIMS, is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less, and even more preferably 10,000 or less. In a preferred embodiment, it is 5,000 or less, more preferably 1,000 to 4,000, and even more preferably 1,000 to 3,800. Within such ranges, the effect of preventing corrosion and deterioration is excellent.

[0208] In this description, the purge rate is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeters per Minute), more preferably 2,000 to 30,000 sccm, and even more preferably 2,500 to 15,000 sccm. Within this range, the thin film growth rate per cycle is appropriately controlled, and deposition is performed to a single atomic layer or close to it, which is advantageous in terms of film quality.

[0209]

[0210] ALD (atomic layer deposition) is extremely advantageous in the manufacture of integrated circuits (ICs) that require high aspect ratios, and has advantages such as excellent conformality, uniformity, and precise thickness control due to its self-limiting thin film growth mechanism.

[0211] The thin film formation method may be performed at a deposition temperature in the range of, for example, 50 to 800° C., preferably 300 to 700° C., more preferably 400 to 650° C., even more preferably 400 to 600° C., and even more preferably 450 to 600° C. Within this range, there is an effect of growing a thin film with excellent film quality while implementing the characteristics of the ALD process.

[0212] The thin film forming method may be carried out at a deposition pressure in the range of, for example, 0.01 to 20 Torr, preferably 0.1 to 20 Torr, more preferably 0.1 to 10 Torr, and most preferably 1 to 7 Torr, which is effective in obtaining a thin film of uniform thickness.

[0213] In this description, deposition temperature and deposition pressure may be measured at the temperature and pressure established within a deposition chamber or at the temperature and pressure applied to a substrate within a deposition chamber.

[0214] The thin film forming method may preferably include a step of raising the temperature in the chamber to a deposition temperature before introducing the shielding compound into the chamber; and / or a step of injecting an inert gas into the chamber to purge the chamber before introducing the shielding compound into the chamber.

[0215] The present invention may also include a thin film manufacturing apparatus capable of implementing the thin film manufacturing method, the thin film manufacturing apparatus including an ALD chamber, a first vaporizer for vaporizing a shielding compound, a first transfer means for transferring the vaporized shielding compound into the ALD chamber, a second vaporizer for vaporizing a thin film precursor, and a second transfer means for transferring the vaporized thin film precursor into the ALD chamber. Here, the vaporizer and the transfer means are not particularly limited as long as they are vaporizers and transfer means commonly used in the technical field to which the present invention pertains.

[0216]

[0217] As a specific example, the method of forming the thin film will be described. First, a substrate on which a thin film can be formed is placed in a deposition chamber capable of atomic layer deposition.

[0218] The substrate may include a semiconductor substrate such as a silicon substrate, silicon oxide substrate, or the like.

[0219] The substrate may further have a conductive or insulating layer formed thereon.

[0220] In order to deposit a thin film on a substrate placed in the deposition chamber, the above-mentioned shielding compound and precursor compound, or a mixture thereof with a non-polar solvent, are prepared.

[0221] The prepared shielding compound is then injected into a vaporizer, transformed into a vapor phase, and delivered to a deposition chamber to be adsorbed onto a substrate, followed by purging to remove any unadsorbed shielding compound.

[0222] Next, the prepared precursor compound or a mixture of the precursor compound and a non-polar solvent (thin film forming composition) is injected into a vaporizer, converted into a vapor phase, and delivered to a deposition chamber to be adsorbed onto a substrate, and unadsorbed precursor compound / thin film forming composition is purged.

[0223] In the present description, the steps of adsorbing the shielding compound onto a substrate and then purging to remove any unadsorbed shielding compound; and adsorbing a precursor compound onto a substrate and purging to remove any unadsorbed precursor compound may be performed in a different order, if necessary.

[0224] In this description, the method of delivering the shielding compound and the precursor compound (thin film forming composition) to the deposition chamber may be, for example, a method of delivering a volatilized gas using a mass flow controller (MFC) method (Vapor Flow Control; VFC), or a method of delivering a liquid using a liquid mass flow controller (LMFC) method (Liquid Delivery System; LDS), and preferably the LDS method is used.

[0225] Here, the carrier gas or dilution gas for moving the shielding compound and the precursor compound onto the substrate is argon (Ar), nitrogen (N 2), helium (He), or a mixture of two or more gases may be used, but is not limited thereto.

[0226] As the purge gas in this description, for example, an inert gas may be used, and preferably, the carrier gas or diluent gas may be used.

[0227]

[0228] Next, a reaction gas is supplied. The reaction gas is not particularly limited as long as it is a reaction gas commonly used in the technical field to which the present invention pertains, and may preferably contain a nitriding agent. The nitriding agent reacts with the precursor compound adsorbed on the substrate to form a nitride film.

[0229] Preferably, the nitriding agent is nitrogen gas (N 2 ), hydrazine gas (N 2 H 4 ), or a mixture of nitrogen gas and hydrogen gas.

[0230] Next, the remaining unreacted reactant gas is purged with an inert gas, which removes not only the excess reactant gas but also any by-products that are produced.

[0231] As described above, the thin film formation method may, for example, have a unit cycle including the steps of shielding the shielding compound on the substrate, purging the unadsorbed shielding compound, adsorbing the precursor compound / thin film forming composition on the substrate, purging the unadsorbed precursor compound / thin film forming composition, supplying a reactive gas, and purging the remaining reactive gas, and the unit cycle may be repeated to form a thin film of a desired thickness.

[0232] As another example, the thin film formation method may be configured such that a unit cycle includes a step of adsorbing a precursor compound / thin film forming composition onto a substrate, a step of purging unadsorbed precursor compound / thin film forming composition, a step of adsorbing a shielding compound onto a substrate, a step of purging unadsorbed shielding compound, a step of supplying a reactive gas, and a step of purging residual reactive gas, and the unit cycle is repeated to form a thin film of a desired thickness.

[0233] For example, the unit cycle may be repeated 1 to 99,999 times, preferably 10 to 1,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times, and within this range, the desired thin film characteristics are effectively expressed.

[0234]

[0235] The present invention also provides a semiconductor substrate, characterized in that the semiconductor substrate is manufactured by the thin film formation method described herein. In this case, the thin film has excellent step coverage and thickness uniformity, and has excellent density and electrical properties.

[0236] The thin film thus produced preferably has a thickness of 20 nm or less, a resistivity of 50 to 400 μΩ cm based on a 10 nm thin film thickness, a halogen content of 10,000 ppm or less, and a step coverage rate of 90% or more. Within these ranges, the thin film has excellent performance as a diffusion barrier film and is effective in reducing corrosion of metal wiring materials, but is not limited thereto.

[0237] The thin film may have a thickness of, for example, 0.1 to 20 nm, preferably 1 to 20 nm, more preferably 3 to 25 nm, and even more preferably 5 to 20 nm, and within this range, there is an effect of excellent thin film properties.

[0238] For example, the thin film may have a resistance value of 0.1 to 400 μΩ·cm, preferably 15 to 300 μΩ·cm, more preferably 20 to 290 μΩ·cm, and even more preferably 25 to 280 μΩ·cm, based on a thin film thickness of 10 nm, and has the effect of exhibiting excellent thin film properties within this range.

[0239] The thin film may have a halogen content of preferably 10,000 ppm or less, or 1 to 9,000 ppm, more preferably 5 to 8,500 ppm, and even more preferably 100 to 1,000 ppm. Within this range, the thin film has excellent thin film properties and a reduced thin film growth rate. Here, the halogen remaining in the thin film is, for example, Cl. 2 , Cl, or Cl - The lower the amount of residual halogen in the thin film, the better the film quality will be, which is preferable.

[0240] As an example, the thin film has a step coverage of 90% or more, preferably 92% or more, and more preferably 95% or more. Within this range, even thin films with complex structures can be easily deposited onto a substrate, and this has the advantage that the thin films can be applied to next-generation semiconductor devices.

[0241]

[0242] The thin film may have a multilayer structure of two or three layers as required, for example. The multilayer film having a two-layer structure may have a lower layer film-middle layer film structure, and the multilayer film having a three-layer structure may have a lower layer film-middle layer film-upper layer film structure, for example.

[0243] The underlayer film may be, for example, Si, SiO 2 , MgO, Al 2 O 3 , CaO, ZrSiO 4 , ZrO 2 , HfSiO 4 , Y 2 O 3 , HfO 2 , LaLuO 2 , Si 3 N4 , SrO, La 2 O 3 , Ta 2 O 5 , BaO, TiO 2 The composition may include one or more selected from the group consisting of:

[0244] The intermediate layer is, for example, Ti x N y , preferably including TN.

[0245] The upper layer film may contain at least one selected from the group consisting of W and Mo, for example.

[0246]

[0247] Below, preferred embodiments and drawings are presented to aid in understanding the present invention. However, the following embodiments and drawings are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope of the scope and technical idea of ​​the present invention. Naturally, such changes and modifications also fall within the scope of the appended claims.

[0248]

[0249] [Example]

[0250] Examples 1 to 8, Comparative Examples 1 to 4

[0251] The ALD deposition process was carried out using the components shown in Table 1 below.

[0252] Specifically, as the shielding compounds, compounds represented by the following chemical formulas 1-1 to 1-4, compounds represented by the following chemical formulas 2-1 to 2-4, compounds represented by the following chemical formulas 3-1, and compounds represented by the following chemical formulas 3-2 were prepared.

[0253] [Chemical Formula 1-1 to 1-4]

[0254] [ka]

[0255] [Chemical Formula 2-1 to 2-4]

[0256] [ka]

[0257] [Chemical Formula 3-1 to 3-2]

[0258] [ka]

[0259] The precursor is CpHf(NMe 2 ) 3 ) tris(dimethylamido)cyclopentadienylhafnium (referred to as CpHf in the table below) and Cp(CH 2 ) 3 NM 3 Hf(NMe 2 ) 2 (Methyl-3-cyclopentadienylpropylamino)bis(dimethylamino)hafnium (referred to as H03 in the table below), and TiCl 4 were prepared respectively.

[0260] The prepared shielding compound was placed in a canister and supplied to a vaporizer heated to 150°C at a flow rate of 0.05g / min using an LMFC (Liquid Mass Flow Controller) at room temperature. The shielding compound vaporized in the vapor phase in the vaporizer was introduced into a deposition chamber loaded with a substrate for 1 second, and then argon gas was supplied at 5000sccm for 2 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled at 2.5Torr. Next, the prepared precursor compound was placed in a separate canister and supplied to a separate vaporizer heated to 150°C at a flow rate of 0.05g / min using an LMFC (Liquid Mass Flow Controller) at room temperature. Si vaporized in the vapor phase in the vaporizer 2 Cl 6 was introduced into the deposition chamber for 1 second, and then argon gas was supplied at 5000 sccm for 2 seconds to perform argon purging. At this time, the pressure in the reaction chamber was controlled at 2.5 Torr.

[0261] Next, 1000 sccm of ammonia or ozone as a reactive gas was introduced into the reaction chamber for 3 seconds, and then argon purging was performed for 3 seconds. At this time, the substrate on which the metal thin film was to be formed was heated under the temperature conditions shown in Table 1 below.

[0262] This process was repeated 200 to 400 times to form a self-limiting atomic layer thin film having a thickness of 10 nm.

[0263] For each of the obtained thin films of Examples 1 to 8 and Comparative Examples 1 to 4, the deposition rate reduction rate (D / R reduction rate) and SIMS C impurity were measured in the following manner, and the results are shown in Table 1 and FIGS. 1 and 2.

[0264] *Deposition rate reduction rate (D / R (dep.rate) reduction rate): This refers to the ratio of the deposition rate reduction after the addition of the shielding agent compared to the D / R before the addition of the shielding agent, and was calculated as a percentage using the measured A / cycle values.

[0265] Specifically, the reduction rate of the thin film growth rate was calculated by dividing the thickness of the thin film measured by an ellipsometer, which is a device capable of measuring optical properties such as the thickness and refractive index of the thin film using the polarization properties of light, by the number of cycles to calculate the thickness of the thin film deposited per cycle. Specifically, it was calculated using the following Equation 1.

[0266] [Formula 1]

[0267]

number

[0268] (In the above formula, DRn is a depth rate measured for a thin film prepared without adding the shielding compound, and DRw is a depth rate measured for a thin film prepared with adding the shielding compound, where the depth rate is a value measured for a thin film having a thickness of 3 to 30 nm under normal temperature and pressure conditions using an ellipsometer device, and is expressed in Å / cycle units.)

[0269] *SIMS (Secondary-ion mass spectrometry) C impurity: The C impurity value was confirmed on the SIMS graph, taking into account the C impurity counts at a sputter time of 50 seconds, when the thin film is penetrated in the axial direction by ion sputtering and there is little contamination in the substrate surface layer.

[0270] [Table 1]

[0271] As shown in Table 1 and Figures 1 and 2, Example 4 using the shielding compound according to the present invention not only exhibited a significantly improved deposition rate reduction rate, but also exhibited excellent impurity reduction characteristics, as compared to Comparative Example 4 not using the shielding compound according to the present invention. Also, Examples 1 to 3 and 5 to 8 using the shielding compound according to the present invention not only exhibited a significantly improved deposition rate reduction rate, but also exhibited excellent impurity reduction characteristics, as compared to Comparative Examples 1 to 3 using other types of shielding compounds deviating from the appropriate types, such as THF and CPME.

[0272] In particular, it was confirmed that Examples 1 to 8, which used the shielding compound according to the present invention, showed a reduction rate of the thin film growth rate per cycle of 20% or more compared to Comparative Example 4, which did not use the shielding compound, or Comparative Examples 1 to 3, which used THF or CPME.

[0273]

[0274] Additional experimental examples

[0275] Confirmation of oxidation degree inside the thin film

[0276] In order to confirm the internal state of the thin film produced in Example 8 and the thin film produced in Comparative Example 3, the ratio of oxygen (O) to hafnium (Hf) was analyzed.

[0277] Specifically, the thin films of about 10 nm thickness prepared in Example 8 and Comparative Example 3 were analyzed for Hf and O elements through XPS (X-ray Photoelectron Spectroscopy) while penetrating into the depth direction, and the element ratio (at%) of Hf and O elements was converted to a ratio (O / Hf ratio) and shown in the following Figures 3 and 4.

[0278] FIG. 3 is a graph showing the ratio of oxygen (O) to hafnium (Hf) in the thin film produced in Comparative Example 3, and FIG. 4 is a graph showing the ratio of oxygen (O) to hafnium (Hf) in the thin film produced in Example 8. As the etch time increases, the amount of HfO 2 This refers to the oxidation state deep inside the thin film.

[0279] As shown in Figure 4 below, when the deposition rate (D / R) of the shielding compound of formula 2-1 was significantly reduced to 88.5%, the reactant O 3 It can be seen that the number of times the substrate is exposed to the air is 2 to 4 times greater than in the past, so sufficient oxidation is achieved.

[0280] For reference, the presence of metallic Hf can cause a problem of lowering the dielectric constant, which is extremely important as a dielectric. 2 The stoichiometric ratio of is hafnium (1): oxygen (2), and the O / Hf ratio before application of the shielding agent corresponds to 1.9 as a result of simulation. Looking at the midpoint of the 5 nm thickness (etch time @ 150 sec) where there is no external influence in the depth direction of the 10 nm thin film in which the compound of Formula 2-1 in Example 8 is applied as a shielding agent, it is analyzed that the O / Hf ratio is 2.0, as it is oxidized by 10% more than before application of the shielding agent.

[0281] Meanwhile, as shown in Figure 3 below, when the deposition rate (D / R) is reduced by using the shielding compound of formula 3-2, it can be seen that Hf is insufficiently oxidized compared to the conventional process in which no shielding agent is used. 2 Reflecting the stoichiometric ratio of and the simulated O / Hf ratio value of 1.9 before application of the shielding agent, when the compound of Formula 3-2 in Comparative Example 3 is applied as a shielding agent, the midpoint of the 5 nm thickness (etch time @ 200 sec) where there is no external influence in the depth direction of the 10 nm thin film is analyzed to be 3.75% less oxidized than before application of the CPME shielding agent, and the O / Hf ratio is analyzed to be 1.83.

[0282] In other words, if the dotted line is relatively higher than the solid line, it can be considered to be closer to HfO2.0, and the higher it is, the more preferable it is. This shows that the degree of oxidation inside the thin film is effectively improved when the shielding compound of the present invention is applied.

[0283]

[0284] Evaluation of step coverage and thickness uniformity

[0285] The step coverage characteristics of the thin films prepared in Examples 4 and 5 were confirmed.

[0286] Figure 5 below shows TEM measurement images of test pieces cut horizontally at a position 100 nm below the top of a thin film deposited under the conditions of Example 4 on a substrate with a complex structure and an aspect ratio of 22:1 (left drawing) and at a position 100 nm above the bottom (right drawing).

[0287] Specifically, a deposition process was performed under conditions for applying the shielding agent of Example 4 to a substrate having a complex structure with an aspect ratio of 22:1, with an upper diameter of 90 nm, a lower diameter of 65 nm, and a via hole depth of about 2000 nm.

[0288] To confirm the uniformity of the deposited thickness and step coverage inside the vertically formed via hole, test pieces were cut horizontally at a position 100 nm below the top and 100 nm above the bottom, and were measured using a transmission electron microscope (TEM).

[0289] Here, a diagram measured at a position 100 nm below from the top is shown in the left diagram of FIG. 5, and a diagram measured at a position 100 nm above from the bottom is shown in the right diagram of FIG.

[0290] In Figure 5 below, the thin base is SiO 2 , dark black is HfO 2 Considering that the thickness of about 8 nm was deposited on the upper inner wall of the via hole and the thickness of about 1.5 nm was deposited on the lower inner wall, the step coverage was analyzed to be 18.75%.

[0291] In particular, as shown in the right-hand drawing, the continuity of the black lines is lacking, which indicates the absence of uniformity in a narrow, deep, and complex structure.

[0292]

[0293] FIG. 6 below shows TEM images of specimens cut horizontally at a position 100 nm below the top of a thin film deposited under the conditions of applying the shielding compound of Chemical Formula 1-3 in Example 5 on a substrate with a complex structure having an aspect ratio of 22:1 (left side drawing) and at a position 100 nm above the bottom (right side drawing).

[0294] Specifically, a deposition process was performed under conditions for applying the shielding agent of Example 4 to a substrate having a complex structure with an aspect ratio of 22:1, with an upper diameter of 90 nm, a lower diameter of 65 nm, and a via hole depth of about 2000 nm.

[0295] To confirm the uniformity of the deposited thickness and step coverage inside the vertically formed via hole, test pieces were cut horizontally at a position 100 nm below the top and 100 nm above the bottom, and were measured using a transmission electron microscope (TEM).

[0296] Here, a diagram showing measurements taken at a position 100 nm below the top is shown in the left diagram of FIG. 6, and a diagram showing measurements taken at a position 100 nm above the bottom is shown in the right diagram of FIG.

[0297] In Figure 6 below, the thin base is SiO 2 , dark black is HfO 2 Considering that the thickness of the deposited film on the upper inner wall of the via hole was about 7.7 nm and the thickness of the deposited film on the lower inner wall was about 7.6 nm, the step coverage was analyzed to be 98.7%.

[0298] In particular, the continuity of the black lines is clear in both the left and right drawings, which indicates excellent uniformity in narrow, deep, and complex structures.

[0299]

[0300] As a result of examining the step coverage and thickness uniformity as described above, it was confirmed that, among Example 4 using the shielding compound of Chemical Formula 2-1 and Example 5 using the shielding compound of Chemical Formula 1-3, Example 5 provided improved step coverage and thickness uniformity compared to Example 4.

[0301]

[0302] Thin film crystalline

[0303] XRD analysis was performed on Comparative Example 4, in which no shielding compound was added, and on Example 1, in which the shielding compound was added in an amount of 0.1 g / min before the addition of the thin film precursor compound. The results are shown in FIG. 7 below.

[0304] FIG. 7 below shows the XRD crystal patterns of Comparative Example 4 (black) and Example 1 (blue).

[0305] As shown in FIG. 7 below, in Example 1, when the shielding compound was added at a rate of 0.1 g / min before the addition of the thin film precursor compound, it was confirmed that the crystal grains of the thin film became larger, i.e., the crystallinity increased.

[0306] Here, the grain size is HfO 2 This can be confirmed by the width of the peak at 31.5° in the thin film, and the narrower the peak, the higher the crystallinity, and the increased crystallinity has the advantage of greatly improving the dielectric constant. Additionally, the characteristic peak of the tetragonal system, which has the highest dielectric constant among monoclinic, orthorhombic, and tetragonal, was observed at 30.5°.

[0307]

[0308] Thin film density

[0309] X-ray reflectometry (XRR) analysis was performed on the sample in which no shielding compound was added as in Comparative Example 4, and on the sample in which the shielding compound was added in an amount of 0.1 g / min before the addition of the thin film precursor compound as in Example 4, and the measurement results are shown in Table 1 below.

[0310] In addition, the same process as in Example 4 was repeated except that the deposition temperature was changed to 340°C and 420°C, and then a reflectometry (XRR) analysis was performed. The measurement results are shown in Example 4-1 and Example 4-2, respectively.

[0311] Further, the same process as in Comparative Example 4 was repeated except that the deposition temperature was changed to 380°C and 420°C, and then a reflectometry (XRR) analysis was performed. The measurement results are shown in Comparative Example 4-1 and Comparative Example 4-2, respectively.

[0312] [Table 2]

[0313] As shown in Table 2, in each of Examples 4, 4-1, and 4-2, the shielding compound was added in an amount of 0.1 g / min before the addition of the thin film precursor compound to shield the thin film. As a result, it was confirmed that the thin film density was significantly improved compared to all of Comparative Examples 4, 4-1, and 4-2.

[0314] Therefore, according to the present invention, a compound having a predetermined structure is provided as a shielding agent, and a deposition layer of a uniform thickness is formed on a substrate as a shielding region according to the difference in the adsorption distribution pattern of the shielding agent, thereby reducing the deposition rate of the thin film, and appropriately lowering the thin film growth rate, thereby significantly improving step coverage and thin film thickness uniformity even when a thin film is formed on a substrate having a complex structure, and significantly reducing impurities. A shielding compound, a thin film formation method using the same, and a semiconductor substrate and a semiconductor device manufactured therefrom can be provided.

Claims

1. A shielding compound comprising a linear or cyclic saturated or unsaturated hydrocarbon having two or more of nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) and having 3 to 15 carbon atoms.

2. The shielding compound according to claim 1, characterized in that the shielding compound has a structure containing nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) at both ends of a central carbon atom connected to oxygen by a double bond.

3. The thin film shielding compound according to claim 1, characterized in that it has a structure containing nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) at one end of a central carbon atom connected to oxygen by a double bond and carbon (C) at the other end.

4. The shielding compound according to claim 1 , wherein the shielding compound is at least one selected from the group consisting of a compound represented by the following Formula 1 and a compound represented by the following Formula 2: [Chemical formula 1] 【Chemistry 1】 [Chemical formula 2] 【Chemistry 2】 (A is oxygen (O), sulfur (S), phosphorus (P), nitrogen (N), -CH, or -CH ２ and B is —OH, —OCH ３ , -OCH ２ CH ３ , -CH ２ CH ３ , -SH, -SCH ３ , or -SCH ２ CH ３ wherein R' and R'' are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and n is an integer of 0 to 3.

5. The shielding compound according to claim 1, wherein the shielding compound is at least one selected from the group consisting of compounds represented by the following formulas 1-1 to 1-4 and 2-1 to 2-4. [Chemical Formulas 1-1 to 1-4] 【Chemistry 3】 [Chemical Formulas 2-1 to 2-4] 【Chemistry 4】

6. 2. The shielding compound according to claim 1, wherein the shielding compound provides a shielding region for an oxide film, a nitride film, a metal film, or a selective thin film thereof, and the shielding region is formed on the entire substrate or a portion of the substrate on which the oxide film, the nitride film, the metal film, or a selective thin film thereof is formed.

7. The shielding compound according to claim 6, wherein the shielded region occupies 10 to 95% of the total area of ​​the entire substrate or the partial substrate, and the unshielded region occupies the remaining area, when the total area of ​​the substrate is 100%.

8. The shielding compound according to claim 1, characterized in that the thin film is a laminated film of one or more elements selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce and Nd.

9. The shielding compound according to claim 1 , wherein the thin film is used as a diffusion barrier film, an etching stop film, an electrode film, a dielectric film, a gate insulating film, a block oxide film, or a charge trap.

10. 1. A method for forming a thin film, comprising: injecting a shielding compound represented by the following Formula 1 or 2 into a chamber to shield a surface of a loaded substrate: [Chemical formula 1] 【Chemistry 5】 [Chemical formula 2] 【Chemistry 6】 (A is oxygen (O), sulfur (S), phosphorus (P), nitrogen (N), -CH, or -CH ２ and B is —OH, —OCH ３ , -OCH ２ CH ３ , -CH ２ CH ３ , -SH, -SCH ３ , or -SCH ２ CH ３ wherein R' and R'' are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and n is an integer of 0 to 3.

11. 11. The method of claim 10, wherein the chamber is an ALD chamber, a CVD chamber, a PEALD chamber or a PECVD chamber.

12. 11. The method of claim 10, wherein the shielding compound is transferred into the chamber by a VFC method, a DLI method, or an LDS method, and the thin film is a silicon nitride film, a silicon oxide film, a titanium nitride film, a titanium oxide film, a tungsten nitride film, a molybdenum nitride film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, or an aluminum oxide film.

13. A semiconductor substrate manufactured by the thin film forming method according to claim 10.

14. The semiconductor substrate according to claim 13, wherein the thin film has a multi-layer structure of two or three layers.

15. A semiconductor device comprising the semiconductor substrate of claim 14.

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