KR20230120968A - A reaction surface control agent for oxidation thin film, method for forming oxidation thin film using the same, semiconductor substrate and semiconductor device prepared therefrom - Google Patents

Abstract

The present invention relates to a reaction surface control agent for an oxide film, a method of forming an oxide film using the same, and a semiconductor substrate and a semiconductor device prepared therefrom, wherein a compound of a predetermined structure is provided as an oxide film reaction surface control agent to form a deposited layer of uniform thickness due to differences in the adsorption distribution of the oxide film reaction surface control agent as a barrier region on a substrate, so that the deposition rate of a thin film is reduced and the growth rate of the thin film is appropriately lowered, and thus, the step coverage and thickness uniformity of the thin film can be greatly improved and impurities can be reduced even when the thin film is formed on a substrate with a complex structure.

Description

Oxide film reaction surface control agent, method of forming oxide film using the same, semiconductor substrate and semiconductor device manufactured therefrom

The present invention relates to an oxide film reaction surface control agent, a method of forming an oxide film using the same, and a semiconductor substrate and a semiconductor device manufactured therefrom, and more particularly, a compound having a predetermined structure is provided as an oxide film reaction surface control agent to obtain a homogeneous structure due to a difference in adsorption distribution. By forming a thick deposited layer on the substrate as a shielding area, the deposition rate of the thin film is reduced and the growth rate of the thin film is appropriately lowered to ensure step coverage and thickness uniformity of the thin film even when a thin film is formed on a substrate having a complicated structure. It relates to an oxide film reaction surface control agent capable of greatly improving and greatly reducing impurities, a method of forming an oxide film using the same, and a semiconductor substrate manufactured therefrom.

Due to the improvement in the degree of integration of memory and non-memory semiconductor devices, the fine structure of a substrate is becoming more complex day by day.

For example, the width and depth of the microstructure (hereinafter referred to as 'aspect ratio') is increasing to 20:1 or more and 100:1 or more, and the larger the aspect ratio, the more difficult it is to form a sedimentary layer with a uniform thickness along the complex microstructure surface. There is a problem that gets difficult.

As a result, the step coverage (step coverage), which defines the thickness ratio of the upper and lower layers in the depth direction of the microstructure, remains at the 90% level, making it increasingly difficult to express the electrical characteristics of the device. is increasing Since the step coverage of 100% means that the thickness of the deposited layers formed on the top and bottom of the microstructure is the same, it is necessary to develop technology so that the step coverage approaches 100% as much as possible.

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

The thin film is generally used as a diffusion barrier between a silicon layer of a doped semiconductor and aluminum (Al) or copper (Cu) used as an interlayer wiring material. However, when depositing a tungsten (W) thin film on a substrate, it is used as an adhesion layer.

As discussed above, in order to obtain excellent and uniform physical properties of a thin film deposited on a substrate, high step coverage of the thin film is essential, so ALD (atomic layer deposition) process is utilized, but there is still a problem in realizing 100% step coverage.

When the deposition temperature is raised for the purpose of realizing 100% step coverage, the step coverage is difficult. First of all, in the deposition process consisting of a precursor and a reactant, an increase in the deposition temperature leads to a steep increase in the thin film growth rate (GPC). In addition, even if the ALD process is performed at 300 ° C. to mitigate the increase in GPC due to the increase in deposition temperature, since the deposition temperature increases during the process, it is difficult to call it a solution.

In addition, a high-temperature process is required to realize a metal oxide film of excellent film quality in a semiconductor device. Research results have been reported that the concentration of carbon and hydrogen remaining in the thin film is reduced by increasing the atomic layer deposition temperature up to 400 ° C (refer to the paper J. Vac. Sci. Technol. A, 35 (2017) 01B130).

However, the higher the deposition temperature, the more difficult it is to secure the step coverage. First, in a deposition process composed of a precursor and two reactants, an increase in deposition temperature may result in a rapid increase in GPC (thin film growth rate). In addition, it has been confirmed that GPC increases by about 10% at 300° C. even when a known shielding agent is applied to mitigate the increase in GPC due to an increase in deposition temperature. That is, when depositing at 360° C. or higher, it is difficult to expect the GPC reduction effect provided by conventionally known shielding agents.

Therefore, it is possible to form a thin film with a complex structure effectively even at a high temperature, a low residual amount of impurities, and a method of forming a thin film that greatly improves step coverage and thickness uniformity of the thin film, and a semiconductor substrate manufactured therefrom. It is in need of development.

In order to solve the problems of the prior art as described above, the present invention reduces the deposition rate of the thin film and increases the growth rate of the thin film by forming a uniform thickness of the deposited layer on the substrate due to the difference in the adsorption distribution of the oxide film reaction surface control agent as a shielding area for the thin film. Provision of an oxide film reaction surface control agent that greatly improves step coverage and thickness uniformity of a thin film even when a thin film is formed on a substrate having a complex structure by appropriately lowering it, a method of forming an oxide film using the same, and a semiconductor substrate manufactured therefrom aims to do

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

The above and other objects of the present invention can all be achieved by the present invention described below.

In order to achieve the above object, the present invention includes at least one compound selected from among cyclic compounds having three or more elemental species having unshared electron pairs and linear compounds having three or more elemental species having unshared electron pairs, Provided is an oxide film reaction surface control agent characterized by controlling a reaction surface of an oxide film composed of at least one metal selected from among a valent metal, a tetravalent metal, a pentavalent metal, and a hexavalent metal.

The unshared electron pair may be at least one selected from oxygen (O), sulfur (S), phosphorus (P), and nitrogen (N).

The cyclic compound having three or more elemental species having unshared electron pairs may be a compound represented by Formula 1 below.

[Formula 1]

(In Formula 1, R' is 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,

A is oxygen (O), sulfur (S), phosphorus (P), or nitrogen (N),

The m is an integer from 0 to 2.)

The linear compound having three or more elemental species having unshared electron pairs may be a compound represented by Formula 2 below.

[Formula 2]

(In Formula 2, R ^” is 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,

B is -OH, -OCH ₃ , -OCH ₂ CH ₃ , -CH ₂ CH ₃ , -SH, -SCH ₃ , or -SCH ₂ CH ₃ .)

The oxide film reaction surface control agent may have a refractive index (measured at 20 to 25 ° C) of 1.365 to 1.48, 1.366 to 1.47, 1.367 to 1.46, 1.365 to 1.41, or 1.41 to 1.46.

The oxide layer reaction surface controller may include one or more compounds selected from compounds represented by Chemical Formulas 1-1 to 1-3 and Chemical Formulas 2-1 to 2-3.

[Formula 1-1 to 1-3]

, ,

[Formula 2-1 to 2-3

, ,

The metals are 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 can control the reaction surface of the oxide film formed from one or more precursor compounds selected from the group consisting of.

In addition, the present invention

treating the surface of the substrate with the above-described oxide film reaction surface control agent; and

Forming an oxide film on the surface of the loaded substrate by sequentially injecting a precursor compound and a reactive gas into a chamber on the treated substrate;

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

The substrate surface treatment step may be performed by applying the oxide film reaction surface control agent to the substrate loaded in the chamber at 20 to 800 °C.

The oxide film reaction surface control agent and the precursor compound are transferred into the chamber by a VFC method, a DLI method, or an LDS method, and the thin film is a silicon oxide film, a titanium oxide film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, an aluminum oxide film, It may be a niobium oxide film or a thallium oxide film.

The reaction gas may include O2, O3, N2O, NO2, H2O, or O2 plasma.

The oxide film is 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 may be a thin film in which one or more layers are stacked.

The thin film may be a diffusion barrier layer, an etch stop layer, an electrode layer, a dielectric layer, a gate insulating layer, a block oxide layer, or a charge trap.

The oxide film formation method,

i) forming a shielding region on the surface of the substrate loaded into the chamber by evaporating the above-mentioned oxide film reaction surface control agent;

ii) first purging the inside of the chamber with a purge gas;

iii) vaporizing the precursor compound and adsorbing it to an area outside the shielding area;

iv) secondarily purging the inside of the chamber with a purge gas;

v) supplying a reactive gas into the chamber; and

vi) tertiary purging the inside of the chamber with a purge gas;

The substrate having the reactive surface activated in the reactive surface activation step may be prepared by applying the oxide film reactive surface control agent to a substrate loaded in a chamber at 20 to 800 °C.

The precursor compound is Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, It is a molecule composed of at least one selected from the group consisting of Re, Os, Ir, La, Ce, and Nd, and may be a precursor having a vapor pressure of greater than 0.01 mTorr and less than 100 Torr at 25 °C.

The precursor compound or precursor compound may be vaporized and injected, followed by plasma post-treatment.

In steps ii) and iv), the amount of the purge gas introduced into the chamber may be 10 to 100,000 times greater than the volume of the oxide layer reaction surface control agent.

The reaction gas is an oxidizing agent, and the reaction gas, the oxide layer reaction surface control agent, and the precursor compound may be transferred into the chamber by a VFC method, a DLI method, or an LDS method.

The substrate loaded into the chamber is heated at 100 to 800 ° C., and a ratio of the oxide film reaction surface control agent and the precursor compound in the chamber (mg/cycle) may be 1: 1 to 1: 20.

In addition, the present invention provides a semiconductor substrate characterized by comprising an oxide film produced by the above-described oxide film formation method.

The oxide film may have a multi-layer structure of two or three layers.

In addition, the present invention provides a semiconductor device including the semiconductor substrate described above.

The semiconductor substrate includes low resistive metal gate interconnects, a high aspect ratio 3D metal-insulator-metal (MIM) capacitor, and a DRAM trench capacitor. , 3D Gate-All-Around (GAA), or 3D NAND flash memory.

According to the present invention, the effect of providing an oxide film reaction surface control agent that improves step coverage even when a thin film is formed on a substrate having a complicated structure by effectively shielding adsorption on the substrate surface to reduce the reaction rate and appropriately lowering the thin film growth rate there is.

In addition, process by-products are more effectively reduced during thin film formation, thereby preventing corrosion or deterioration and improving the crystallinity of the thin film by reforming the film quality, thereby improving the electrical properties of the thin film.

In addition, process by-products are reduced during thin film formation, step coverage and thin film density can be improved, and furthermore, there is an effect of providing an oxide film formation method using the same and a semiconductor substrate manufactured therefrom.

1 is a diagram schematically showing a deposition process sequence based on one cycle according to the present invention.
Figure 2 shows the thickness deposited on the top (100 nm below the top) and the bottom (100 nm above the bottom) of the cross section of the oxide film deposited without using the oxide film reaction surface control agent according to Comparative Example 1, and the deposited using the oxide film reaction surface control agent. These are TEM images of the deposited thickness at the top (100 nm below the top) and bottom (100 nm above the bottom) of the cross-section of the oxide film.
3 is a cross section of an oxide film deposited using an oxide film reaction surface control agent according to Example 3, and the thickness deposited at the top (100 nm below the top) and the bottom (100 nm above the bottom), and the oxide film deposited using the oxide film reaction surface control agent. TEM pictures of the thickness deposited at the top (100 nm below the top) and bottom (100 nm above the bottom) of the cross-section of .

Hereinafter, the oxide film reaction surface control agent of the present disclosure, a method of forming an oxide film using the same, and a semiconductor substrate manufactured therefrom will be described in detail.

In this description, unless otherwise specified, the term “reaction surface control” means that the substrate surface to be used as a reaction surface in the deposition process is controlled so that the precursor compound is adsorbed to the substrate surface at a reduced reaction rate.

In this description, unless otherwise specified, the term “shielding” means not only reducing, preventing, or blocking the adsorption of precursor compounds for forming a thin film on a substrate, but also reducing, preventing, or blocking adsorption of process by-products on a substrate. means to do

The present inventors use a compound with a predetermined structure as an oxide film reaction surface control agent that will reduce the adsorption rate of the reaction surface where the precursor compound for forming an oxide film reacts on the substrate loaded inside the chamber, and the difference in the adsorption distribution of the oxide film reaction surface control agent A deposited layer of uniform thickness is formed as a shielding area that does not remain in the thin film to form a relatively thin thin film, and at the same time, the growth rate of the formed thin film is greatly reduced. It was confirmed that the coverage is greatly improved, it can be deposited with a particularly thin thickness, and the residual amount of O, Si, metal, metal oxide remaining as a by-product of the process, and even carbon, which was not easy to reduce in the past, is improved. Based on this, the present invention was completed by concentrating on research on an oxide film reaction surface control agent that provides a shielding area.

The oxide film reaction surface control agent of the present invention controls the reaction surface on which an oxide film is formed on a substrate.

The thin film is, 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, which can be provided as one or more precursors selected from the group consisting of 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.

The thin film may have a film composition of, for example, a silicon oxide film, a titanium oxide film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, an aluminum oxide film, a niobium oxide film, or a thallium oxide film.

The thin film may be used in a semiconductor device for use as an etch stop film, an electrode film, a dielectric film, a gate insulating film, a block oxide film, or a charge trap, as well as a generally used diffusion barrier film.

In the present invention, the precursor compound used to form the thin film is Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, At least one selected from the group consisting of Te, Hf, Ta, W, Re, Os, Ir, La, Ce and Nd is used as the central metal atom (M), C, N, O, H, X (halogen), It is a molecule having at least one ligand composed of Cp (cyclopentadiene) and may be a precursor having a vapor pressure of 1 mTorr to 100 Torr at 25 °C.

As the precursor compound, for example, a compound represented by Formula 3 below may be used.

[Formula 3]

(In Formula 3, M is Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, At least one selected from Ta, W, Re, Os, Ir, La, Ce, and Nd, and L1, L2, L3, and L4 are -H, -X, -R, -OR, -NR2, or Cp (cyclopentadiene ), where -X is F, Cl, Br, or I, and -R is C1-C10 alkyl, C1-C10 alkene, or C1-C10 alkane, which can be linear or cyclic. And, the L1, L2, L3 and L4 may be formed from 2 to 6 depending on the oxidation value of the central metal.)

For example, when the central metal is divalent, L1 and L2 may be attached to the central metal as ligands, and when the central metal is hexavalent, L1, L2, L3, L4, L5, and L6 may be attached to the central metal, and L1 to L2 may be attached to the central metal. Ligands corresponding to L6 may be the same as or different from each other.

M may be a trivalent metal, a tetravalent metal, a pentavalent metal, or a kind corresponding to a hexavalent metal, and is preferably hafnium (Hf), zirconium (Zr), aluminum (Al), niobium (Nb), or tel. It is rurium (Ta), and in this case, it has a large process by-product reduction effect, excellent step coverage , thin film density improvement effect, and excellent electrical properties, insulation and dielectric properties of the thin film.

Wherein L1, L2, L3 and L4 are -R, -X or Cp, which may be the same as or different from each other, wherein -R is a C1-C10 alkyl, a C1-C10 alkene, or a C1-C10 alkane, and is linear or It may have a cyclic structure.

In addition, L1, L2, L3 and L4 may be the same as or different from each other as -NR2 or Cp, where -R is H, C1-C10 alkyl, C1-C10 alkene, C1-C10 alkane, iPr, or It may be tBu.

In Formula 8, L1, L2, L3, and L4 may be -H or -X, which may be the same as or different from each other, wherein -X may be F, Cl, Br, or I.

Specifically, as an example of an aluminum precursor compound, Al(CH ₃ ) ₃ , AlCl ₄ and the like may be used.

Examples of hafnium precursor compounds include tris(dimethylamido)cyclopentadienyl hafnium of CpHf(NMe ₂ ) ₃ ) and (methyl-3-cyclopentadiene of Cp(CH ₂ ) ₃ NM ₃ Hf(NMe ₂ ) _{2 .} Nylpropylamino)bis(dimethylamino)hafnium and the like can be used.

The oxide film reaction surface controller of the present invention can reduce the adsorption rate of the precursor compound to the substrate by previously controlling the reaction surface to adsorb the precursor compound to the substrate.

The shielding area, for example, may be formed on the entire substrate or a portion of the substrate on which the thin film is formed.

Furthermore, when the total area of the entire substrate or part of the substrate is 100% of the total area of the substrate, the shielding area is, for example, 10 to 95% of the area, specifically, 15 to 90% of the area, preferably preferably occupies 20 to 85% of the area, more preferably 30 to 80% of the area, still more preferably 40 to 75% of the area, even more preferably 40 to 70% of the area, and the unshielded area remains It may be that it occupies an area.

Furthermore, when the total area of the entire substrate or part of the substrate is 100% of the total area of the substrate, the first shielding area is 10 to 95% of the area, specifically 15 to 90% of the area, preferably Preferably it occupies 20 to 85% of the area, more preferably 30 to 80% of the area, still more preferably 40 to 75% of the area, even more preferably 40 to 70% of the area, and 10 to 70% of the remaining area 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, still more preferably 40 to 75% of the area, still more preferably The area of 40 to 70% may be occupied by the second shielded area, and the remaining area may be occupied by the unshielded area.

The oxide film reaction surface control agent may provide a controlled reaction surface on the surface of the substrate on which the aforementioned thin film is to be provided.

The oxide layer reaction surface control agent may contain three or more nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S), and may include a linear or cyclic saturated hydrocarbon or a linear saturated hydrocarbon having 3 to 15 carbon atoms. In this case, when forming a thin film, a shielding region that does not remain in the thin film is formed to form a relatively sparse thin film, while at the same time suppressing side reactions and controlling the growth rate of the thin film, process by-products in the thin film are reduced to reduce corrosion or deterioration , the crystallinity of the thin film is improved, it reaches a stoichiometric oxidation state when forming a metal oxide film, and even when a thin film is formed on a substrate having a complex structure, step coverage and thickness uniformity of the thin film are greatly improved has an enhancing effect.

As a specific example, the oxide film reaction surface control agent has a structure independently including nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) at both ends of a central carbon atom connected by a double bond with oxygen. The effect of reducing process by-products is high, and the step coverage is excellent, and the effect of improving the thin film density and the electrical properties of the thin film may be more excellent.

Unless otherwise specified, structures independently containing nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) at both ends of the central carbon atom linked by a double bond with the oxygen described above, refers to

As a specific example, the oxide film reaction surface control agent includes nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) at one end of a central carbon atom linked to oxygen by a double bond, and carbon (C) at the other end. ), the effect of reducing process by-products is high, the step coverage is excellent, and the effect of improving the density of the thin film and the electrical properties of the thin film can be more excellent.

Here, a structure including nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S) at one end of a central carbon atom linked to oxygen by a double bond, and carbon (C) at the other end. Unless otherwise specified, refers to

The oxide film reaction surface control agent is characterized in that it comprises at least one compound selected from a cyclic compound having three or more elemental species having unshared electron pairs and a linear compound having three or more elemental species having unshared electron pairs as a specific example, In this case, a relatively thin thin film is formed by controlling the reaction surface of an oxide film made of one or more metals selected from trivalent metal, tetravalent metal, pentavalent metal, or hexavalent metal, while suppressing side reactions and controlling the growth rate of the thin film. , Corrosion or deterioration is reduced by reducing process by-products in the thin film, crystallinity of the thin film is improved, a stoichiometric oxidation state is reached when forming a metal oxide film, and even when a thin film is formed on a substrate having a complex structure, there is a step difference. There is an effect of greatly improving step coverage and thickness uniformity of the thin film.

The unshared electron pair may be at least one selected from oxygen (O), sulfur (S), phosphorus (P), and nitrogen (N).

The oxide film reaction surface control agent may preferably be at least one selected from the group consisting of a compound represented by Formula 1 and a compound represented by Formula 2 below. At the same time as forming a thin film, side reactions are suppressed and the growth rate of the thin film is controlled to reduce process by-products in the thin film, thereby reducing corrosion or deterioration, improving the crystallinity of the thin film, and even when forming a thin film on a substrate having a complex structure, there is a step difference. Step coverage and thin film thickness uniformity can be greatly improved.

[Formula 1]

(In Formula 1, R' is 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 A is oxygen (O), sulfur (S), Phosphorus (P) or nitrogen (N), wherein m is an integer from 0 to 2.)

The linear compound having three or more elemental species having unshared electron pairs may be a compound represented by Formula 2 below.

[Formula 2]

(In Formula 2, R ^” is 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,

B is -OH, -OCH ₃ , -OCH ₂ CH ₃ , -CH ₂ CH ₃ , -SH, -SCH ₃ , or -SCH ₂ CH ₃ .)

These oxide film reaction surface control agents are provided alone or in the form of a mixed gas, and thus have a high process by-product reduction effect, excellent step coverage, and excellent thin film density improvement effect and electrical properties of the thin film.

In Formula 1, R' is hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkene group having 1 to 5 carbon atoms, preferably hydrogen, an alkyl group having 1 to 3 carbon atoms, or an alkene group having 1 to 3 carbon atoms, In this case, the process by-product reduction effect is high, the step coverage is excellent, the thin film density improvement effect , and the electrical properties, insulation and dielectric properties of the thin film are more excellent.

In Formula 1, A is oxygen (O) or sulfur (S), preferably oxygen (O), and in this case, the effect of reducing process by-products is excellent, and the step coverage is excellent, and the effect of improving the density of the thin film , the thin film It has advantages of superior electrical properties, insulation and dielectric properties.

The m is an integer of 0 to 2, preferably an integer of 1 to 2.

In Formula 2, R” is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and in this case, the effect of reducing process by-products is excellent and the step coverage is excellent, and the effect of improving thin film density and thin film It has the advantage of superior electrical characteristics.

In Formula 2, B is -OCH ₃ , -OCH ₂ CH ₃ , -OCHCH ₃ , -SH, -SCH ₃ , or -SCH ₂ CH ₃ , preferably -OCH ₃ , -OCH ₂ CH ₃ , or -OCHCH ₃ , and in this case, the effect of reducing process by-products is high, the step coverage is excellent, and the thin film density improvement effect and the electrical properties of the thin film are more excellent.

As a specific example, the oxide layer reaction surface control agent may include one or more compounds selected from compounds represented by Chemical Formulas 1-1 to 1-3 and Chemical Formulas 2-1 to 2-3. In this case, the thin film shielding area It provides a high effect of controlling the growth rate of thin films, a large effect of removing process by-products, and an excellent effect of improving step coverage and film quality.

[Formula 1-1 to 1-3]

, ,

[Formula 2-1 to 2-3]

, ,

In the case of using the oxide film reaction surface control agent, a relatively thin film is formed by forming a uniformly thick deposited layer due to the difference in the adsorption distribution of the corresponding activator having the above structure as a shielding area that does not remain in the thin film, and at the same time formed thin film Even if the growth rate of is significantly lowered, even if applied to a substrate with a complex structure, the uniformity of the thin film is secured and the step coverage is greatly improved. It can provide the effect of improving the carbon residue, which was not easy to reduce.

The oxide film reaction surface control agent may have a refractive index of 1.365 to 1.48, 1.366 to 1.393, or 1.367 to 1.391. In this case, the reaction rate is improved by controlling the reaction surface to be provided with an oxide film on the substrate surface in advance, 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 complicated structure. It has the advantage of effectively protecting the surface of the substrate and effectively removing process by-products by preventing adsorption of not only thin film precursors but also process by-products.

The reaction gas may include O ₂ , O ₃ , N ₂ O, NO ₂ , H ₂ O, or O ₂ plasma.

The oxide film is 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 may be a thin film in which one or more layers are stacked.

The oxide film reaction surface control agent may provide a shielding region for a thin film.

The shielding region for the thin film is characterized in that it does not remain in the thin film.

At this time, non-residue means, unless otherwise specified, when analyzing the components by XPS, less than 0.1 atom% of C element, less than 0.1 atom% of Si element, less than 0.1 atom% of N element, halogen It refers to the case where an element is present in less than 0.1 atomic % (atom%). More preferably, in the Secondary-ion mass spectrometry (SIMS) measurement method or X-ray Photoelectron Spectroscopy (XPS) measurement method, which measures by digging into the substrate in the depth direction, C before and after using the oxide film reaction surface control agent under the same deposition conditions , N, Si, and halogen impurities, it is preferable that the intensity change rate of each element species does not exceed 5%.

The oxide layer may include, for example, 100 ppm or less of a halogen compound.

The oxide layer may be used as a diffusion barrier layer, an etch 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.

The oxide film reaction surface control agent and precursor compound may preferably be a compound with a purity of 99.9% or higher, a compound with a purity of 99.95% or higher, or a compound with a purity of 99.99% or higher. It is recommended to use more than 99% of the material as possible because it may remain or cause a side reaction with the precursor or reactant.

The oxide film reaction surface control agent is preferably used in an atomic layer deposition (ALD) process, and in this case, the oxide film reaction surface control agent effectively protects the surface of the substrate and effectively removes process by-products without interfering with the adsorption of precursor compounds. There are benefits to removing it.

The oxide layer reaction surface control agent is preferably a liquid at room temperature (22°C), has a density of 0.8 to 2.5 g/cm ³ or 0.8 to 1.5 g/cm ³ , and has a vapor pressure (20°C) of 0.1 to 300 mmHg or 1 to 300 mmHg. It may be mmHg, and within this range, a shielding area is effectively formed, and step coverage, thickness uniformity of the thin film, and film quality are improved.

More preferably, the oxide layer reaction surface control agent may have a density of 0.75 to 2.0 g/cm ³ or 0.8 to 1.3 g/cm ³ and a vapor pressure (20° C.) of 1 to 260 mmHg, within this range. is effectively formed, and there is an excellent effect in step coverage, thin film thickness uniformity, and film quality improvement.

The oxide film formation method of the present invention comprises the steps of treating the surface of a substrate with the above-mentioned oxide film reaction surface control agent; and forming an oxide film on the surface of the loaded substrate by sequentially injecting a precursor compound and a reactive gas into the chamber to the treated substrate, and in this case, a shielding region for a thin film is formed on the substrate. Thus, even when a thin film is formed on a substrate having a complex structure by reducing the deposition rate of the thin film and appropriately lowering the thin film growth rate, step coverage and thickness uniformity of the thin film are greatly improved.

In the step of treating the surface of the substrate with the oxide film reaction surface control agent, the supply time (Feeding Time, sec) of the oxide film reaction surface control agent to the substrate surface is preferably 0.01 to 10 seconds, more preferably 0.02 to 8 seconds, and more preferably per cycle. It is preferably 0.04 to 6 seconds, more preferably 0.05 to 5 seconds, and within this range, there are advantages in that the thin film growth rate is low, step coverage and economy are excellent.

In the present disclosure, the feeding time of the precursor compound is based on a flow rate of 0.1 to 500 mg/cycle in a chamber volume of 15 to 20 L, and more specifically, a flow rate of 0.8 to 200 mg/cycle in a chamber volume of 18 L. based on cycle.

In a preferred embodiment, the method of forming the oxide film includes: i) vaporizing the oxide film reaction surface control agent and treating the surface of the substrate loaded in the chamber; ii) first purging the inside of the chamber with a purge gas; iii) vaporizing the precursor compound and adsorbing it to the surface of the loaded substrate in the chamber; iv) secondarily purging the inside of the chamber with a purge gas; v) supplying a reactive gas into the chamber; and vi) thirdly purging the inside of the chamber with a purge gas.

At this time, the above steps i) to vi) may be repeated as a unit cycle until a thin film having a desired thickness is obtained, and thus, within one cycle, the oxide film reaction surface control agent of the present invention When added before the precursor compound and adsorbed on the substrate, the thin film growth rate can be appropriately lowered even when deposited at a high temperature, and the process by-products produced are effectively removed, thereby reducing the resistivity of the thin film and greatly improving the step coverage.

In another preferred embodiment, the substrate whose reaction surface is controlled in the reaction surface control step may be manufactured by applying the oxide film reaction surface control agent to a substrate loaded in a chamber at 20 to 800 °C.

In the oxide film formation method of the present invention, as a preferred example, the surface of the substrate can be activated by adding the oxide film reaction surface control agent of the present invention before the precursor compound in one cycle, and then the precursor compound can be introduced and adsorbed on the substrate, , In this case, even if the thin film is deposited at a high temperature, process by-products can be greatly reduced and the step coverage can be greatly improved by appropriately reducing the thin film growth rate, and the resistivity of the thin film can be reduced by increasing the formation of the thin film, and the aspect ratio Even if applied to a large semiconductor device, the thickness uniformity of the thin film is greatly improved, thereby securing the reliability of the semiconductor device.

In the method of forming the oxide film, for example, when the precursor 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 the unit cycle may be performed 10 to 10,000 times, or more Preferably, it may be repeated 50 to 5,000 times, more preferably 100 to 2,000 times, and the effect to be achieved in the present invention can be sufficiently obtained while obtaining a desired thin film thickness within this range.

The precursor compound is Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Consisting of C, N, O, H, X (halogen), Cp (cyclopentadiene) with at least one selected from the group consisting of Re, Os, Ir, La, Ce and Nd as the central metal atom (M) In the case of a precursor having a vapor pressure of 1 mTorr to 100 Torr at 25 ° C. as a molecule having one or more ligands, the effect of forming a shielding region by the above-described oxide film reaction surface control agent can be maximized despite natural oxidation.

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

The thin film may be a silicon oxide film, a titanium oxide film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, an aluminum oxide film, a niobium oxide film, or a thallium oxide film.

In the present invention, the precursor compound or the precursor compound may be vaporized and injected, and then plasma post-processing may be included. In this case, process by-products may be reduced while improving the growth rate of the thin film.

When the oxide film reaction surface control agent is first adsorbed on the substrate, the precursor compound is adsorbed, and then the precursor compound is adsorbed, the amount of purge gas introduced into the chamber in the step of purging the unadsorbed oxide film reaction surface control agent is It is not particularly limited as long as it is in an amount sufficient to remove the unadsorbed oxide film reaction surface control agent, but may be 10 to 100,000 times as an example, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times. By sufficiently removing the unadsorbed oxide film reaction surface control agent, a thin film can be formed evenly and deterioration of the film quality can be prevented. Here, the input amounts of the purge gas and the oxide layer reaction surface control agent are each based on one cycle, and the volume of the oxide layer reaction surface control agent means the volume of the vapor of the oxide layer reaction surface control agent that has been given opportunity.

As a specific example, when the injection amount of the oxide film reaction surface control agent is 200 sccm and the purge gas flow rate is 5000 sccm in the step of purging the unadsorbed oxide film reaction surface control agent, the injection amount of the purge gas is 25 sccm of the oxide film reaction surface control agent injection amount. It is a ship.

In addition, in the step of purging the unadsorbed precursor compound, the amount of purge gas introduced into the chamber is not particularly limited as long as it is an amount sufficient to remove the unadsorbed precursor compound, but for example, the volume of the precursor compound introduced into the chamber It may be 10 to 10,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times based on, and within this range, unadsorbed precursor compounds are sufficiently removed to form a thin film evenly and to prevent deterioration of film quality. It can be prevented. Here, the input amounts of the purge gas and the precursor compound are based on one cycle, respectively, and the volume of the precursor compound means the volume of the vapor of the precursor compound given opportunity.

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

The precursor compound and the precursor compound may be preferably transferred into the chamber by a VFC method, a DLI method or an LDS method, and more preferably transferred into the chamber by an LDS method.

The substrate loaded into the chamber may be heated to 100 to 650 ° C, for example, 150 to 550 ° C, for example, and the oxide film reaction surface control agent or precursor compound may be injected onto the substrate in an unheated or heated state. It may be injected without being heated according to the deposition efficiency, and then the heating conditions may be adjusted during the deposition process. For example, it may be implanted on a substrate at 100 to 650 °C for 1 to 20 seconds.

The ratio of the precursor compound and the oxide layer reaction surface control agent introduced into the chamber (mg/cycle) may be preferably 1:1.5 to 1:20, more preferably 1:2 to 1:15, and still more preferably 1:2 to 1:12, more preferably 1:2.5 to 1:10, and within this range, the effect of improving step coverage and reducing process by-products is great.

In the method for forming an oxide film, for example, when the oxide film reaction surface control agent and the precursor compound are used, the deposition rate reduction rate represented by Equation 1 below may be 45% or more, specifically 48% or more, and preferably 52% or more. In this case, a deposited layer having a uniform thickness is formed on a thin film using the oxide film reaction surface control agent having the above structure to form a relatively coarse thin film, and at the same time, the growth rate of the formed thin film is greatly reduced, so even if applied to a substrate with a complex structure under high temperature, the thin film By securing the uniformity of the step coverage is greatly improved, it can be deposited with a particularly thin thickness, and it can provide the effect of improving O, Si, metal, metal oxide remaining as a process by-product, and even the remaining amount of carbon, which was not easy to reduce in the past. there is.

[Equation 1]

Deposition rate reduction rate = [{(DR _i )-(DR _f )}/(DR _i )]×100

(In the above formula, DR (Deposition rate, Å/cycle) is the rate at which a thin film is deposited. In thin film deposition formed of precursors and reactants, DR _i (initial deposition rate) is the rate of thin film formed without introducing a reactive surface control agent. Deposition rate DR _f (final deposition rate) is the deposition rate of the thin film formed by injecting the oxide film reaction surface control agent during the above process, where the deposition rate (DR) is 3 to 30 nm using an ellipsometer The thickness of the thin film is measured at room temperature and normal pressure, and the unit of Å/cycle is used.)

즉, 증착 속도를 의미하고, 상기 증착 속도는 일례로 Ellipsometery로 3 내지 30 nm 두께의 박막을 상온, 상압 조건에서 박막의 최종 두께를 측정한 후 총 사이클 회수로 나누어 평균 증착 속도로 구할 수 있다.In Equation 1, the thin film growth rate per cycle when using and not using the oxide film reaction surface control agent is the thin film deposition thickness per cycle (

That is, it means a deposition rate, and the deposition rate can be obtained as an average deposition rate by dividing a thin film having a thickness of 3 to 30 nm by, for example, Ellipsometry by measuring the final thickness of the thin film at room temperature and atmospheric pressure conditions and then dividing by the total number of cycles.

In Equation 1, "when the oxide film reaction surface control agent is not used" means a case in which a thin film is produced by adsorbing only a precursor compound on a substrate in a thin film deposition process. It refers to the case where an oxide film is formed by omitting the step of adsorbing the yesterday and the step of purging the unadsorbed oxide film reaction surface control agent.

In the oxide film formation method, the residual halogen intensity (c / s) in a thin film based on a thin film thickness of 100 Å, measured based on SIMS, is preferably 100,000 or less, more preferably 70,000 or less, still more preferably 50,000 or less, and even more preferably 10,000 or less In a preferred embodiment, it may be 5,000 or less, more preferably 1,000 to 4,000, and even more preferably 1,000 to 3,800, and the effect of preventing corrosion and deterioration within this range is excellent.

Purging in the present substrate is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeter per Minute), more preferably 2,000 to 30,000 sccm, still more preferably 2,500 to 15,000 sccm, and within this range, the thin film growth rate per cycle is appropriately controlled, It is deposited as an atomic mono-layer or close to it, which is advantageous in terms of film quality.

The ALD (atomic layer deposition process) is very advantageous in manufacturing an integrated circuit (IC) requiring a high aspect ratio, and in particular, excellent conformality and uniform coverage due to a self-limiting thin film growth mechanism (uniformity) and precise thickness control.

The oxide film forming method may be carried out at a deposition temperature in the range of 50 to 800 ° C., preferably at a deposition temperature in the range of 300 to 700 ° C., more preferably at a deposition temperature in the range of 400 to 650 ° C. , More preferably, it is carried out at a deposition temperature in the range of 400 to 600 ° C, and even more preferably, it is carried out at a deposition temperature in the range of 450 to 600 ° C. has the effect of growing into

The oxide film forming method may be carried out at a deposition pressure in the range of, for example, 0.01 to 20 Torr, preferably at a deposition pressure in the range of 0.1 to 20 Torr, more preferably at a deposition pressure in the range of 0.1 to 10 Torr, most preferably at a deposition pressure in the range of 0.1 to 10 Torr. Preferably, it is carried out at a deposition pressure in the range of 0.3 to 7 Torr, and there is an effect of obtaining a thin film of uniform thickness within this range.

In the present disclosure, the deposition temperature and the deposition pressure may be measured as the temperature and pressure formed in the deposition chamber or the temperature and pressure applied to the substrate in the deposition chamber.

The method of forming the oxide film preferably includes raising the temperature in the chamber to a deposition temperature before introducing the precursor compound into the chamber; and/or purging by injecting an inert gas into the chamber before introducing the precursor compound into the chamber.

In addition, the present invention is a thin film manufacturing apparatus capable of implementing the thin film manufacturing method, including an ALD chamber, a first vaporizer for vaporizing a precursor compound, a first transport means for transferring the vaporized precursor compound into the ALD chamber, and a first vaporizer for vaporizing the thin film precursor. 2 It may include a thin film manufacturing apparatus including a vaporizer and a second transfer means for transferring the vaporized thin film precursor into the ALD chamber. Here, the vaporizer and transfer means are not particularly limited in the case of vaporizers and transfer means commonly used in the technical field to which the present invention belongs.

As a specific example, in the description of the oxide film formation method, first, a substrate on which a thin film is to be formed is placed in a deposition chamber capable of atomic layer deposition.

The substrate may include a semiconductor substrate such as a silicon substrate or silicon oxide.

The substrate may further have a conductive layer or an insulating layer formed thereon.

In order to deposit a thin film on a substrate placed in the deposition chamber, the above-described oxide film reaction surface control agent, a precursor compound, or a mixture of the non-polar solvent and the mixture are prepared.

Thereafter, the prepared oxide film reaction surface control agent is injected into a vaporizer, changed into a vapor phase, transferred to a deposition chamber, and adsorbed on a substrate, and purged to remove unadsorbed oxide film reaction surface control agent.

Next, the prepared precursor compound or a mixture of it and a non-polar solvent (composition for thin film formation) is injected into a vaporizer, converted into a vapor phase, transferred to a deposition chamber, and adsorbed on the substrate, and the unadsorbed precursor compound/composition for thin film formation purging.

In the present substrate, the step of adsorbing the precursor compound on the substrate and then purging to remove the unadsorbed oxide film reaction surface control agent; And the process of adsorbing the precursor compound on the substrate and purging to remove the unadsorbed precursor compound may be performed by changing the order if necessary.

In the present substrate, the oxide film reaction surface control agent, precursor compound, precursor compound (composition for forming a thin film), etc. are delivered to the deposition chamber, for example, by utilizing a mass flow controller (MFC) method to transfer volatilized gas. A liquid delivery system (LDS) may be used by utilizing a vapor flow control (VFC) or a liquid mass flow controller (LMFC) method, preferably using the LDS method. will be.

At this time, the transport gas or diluent gas for moving the oxide film reaction surface control agent, precursor compound, and precursor compound on the substrate is one or two or more selected from the group consisting of argon (Ar), nitrogen (N ₂ ), and helium (He). Mixed gases may be used, but are not limited thereto.

In the present description, an inert gas may be used as the purge gas, for example, and the transport gas or dilution gas may be preferably used.

Next, a reactive gas is supplied. The reaction gas is not particularly limited in the case of a reaction gas commonly used in the technical field to which the present invention pertains, and may preferably include a nitriding agent. An oxide film is formed by reacting the oxidizing agent with the precursor compound adsorbed on the substrate.

Preferably, the oxidizing agent (reactive gas) is O ₂ , O ₃ , N ₂ O, NO ₂ , H ₂ O, or O ₂ plasma.

Next, the unreacted residual reaction gas is purged using an inert gas. Accordingly, it is possible to remove not only the excess reaction gas but also the generated by-products.

As described above, the oxide film formation method includes, for example, processing an oxide film reaction surface control agent on a substrate, shielding a precursor compound on a substrate, purging unadsorbed oxide film reaction surface control agent, precursor compound / thin film formation The step of adsorbing the composition on the substrate, the step of purging the unadsorbed precursor compound/composition for forming a thin film, the step of supplying a reaction gas, and the step of purging the remaining reaction gas are performed as a unit cycle to form a thin film having a desired thickness. For this purpose, the unit cycle may be repeated.

As another example, the oxide film formation method includes adsorbing the precursor compound / composition for forming a thin film on a substrate, purging the unadsorbed precursor compound / composition for forming a thin film, adsorbing an oxide film reaction surface control agent on a substrate, The step of purging the unadsorbed oxide layer reaction surface control agent, the step of supplying the reaction gas, and the step of purging the remaining reaction gas are set as a unit cycle, and the unit cycle may be repeated to form a thin film having a desired thickness.

The unit cycle may be repeated, for example, 1 to 99,999 times, preferably 10 to 1,000 times, more preferably 50 to 5,000 times, and still more preferably 100 to 2,000 times, and within this range, desired thin film properties This effect is well expressed.

The present invention also provides a semiconductor substrate, characterized in that the semiconductor substrate is manufactured by the method of forming an oxide film of the present description, and in this case, the step coverage of the thin film and the thickness uniformity of the thin film are greatly excellent, and the thickness of the thin film is excellent. It has excellent density and electrical properties.

The thin film (oxide film) may have a thickness of, for example, 0.1 to 20 nm, preferably 0.5 to 20 nm, more preferably 1.5 to 15 nm, and even more preferably 2 to 10 nm, within this range. This has an excellent effect.

The thin film may have a carbon impurity content of preferably 5,000 counts/sec or less or 1 to 3,000 counts/sec, more preferably 10 to 1,000 counts/sec, and still more preferably 50 to 500 counts/sec. There is an effect of reducing the thin film growth rate while excellent thin film characteristics within the range.

The thin film has, for example, a step coverage of 90% or more, preferably 92% or more, and more preferably 95% or more. There are applicable benefits.

The prepared thin film preferably has a thickness of 20 nm or less, a dielectric constant of 5 to 29 based on a thin film thickness of 10 nm, a carbon, nitrogen, and halogen content of 5,000 counts/sec or less, and a step coverage of 90 % or more, and within this range, there is an effect of excellent performance as a dielectric film or a blocking film, but is not limited thereto.

The oxide film may have, for example, a multilayer structure of two or three or more layers, preferably a multilayer structure of two or three layers, if necessary. The multilayer film having a two-layer structure may have a lower film-middle layer structure as a specific example, and the multilayer film having a three-layer structure may have a lower film-middle layer-upper layer structure as a specific example.

The lower layer film is, 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 N ₄ , SrO, La ₂ O ₃ , Ta ₂ O ₅ , BaO, TiO ₂ It may be made of including one or more selected from the group consisting of.

The intermediate layer may include, for example, Ti _x N _y , preferably TN.

The upper layer film may include, for example, one or more selected from the group consisting of W and Mo.

The semiconductor substrate includes low resistive metal gate interconnects, a high aspect ratio 3D metal-insulator-metal (MIM) capacitor, and a DRAM trench capacitor. , 3D Gate-All-Around (GAA), or 3D NAND flash memory.

Hereinafter, preferred embodiments and drawings are presented to aid understanding of the present invention, but the following embodiments and drawings are merely illustrative of the present invention, and various changes and modifications are possible within the scope and spirit of the present invention to those skilled in the art. It is obvious in this regard, and it is natural that such variations and modifications fall within the scope of the appended claims.

[Example]

Examples 1 to 7, Comparative Examples 1 to 10

An ALD deposition process was performed according to the process shown in FIG. 1 using the components and process conditions shown in Table 1 below.

1 is a view schematically showing a deposition process sequence according to the present invention mainly for one cycle.

Argon was introduced into the chamber at 5000 ml/min, and the pressure in the chamber was set to 1.5 Torr using a vacuum pump to form a dilute inert atmosphere.

The oxide film reaction surface control agent shown in Table 1 below is put in a canister, the partial pressure and temperature are adjusted so that the injection amount (mg / cycle) is respectively, put into the deposition chamber loaded with the substrate for 1 second, applied to the substrate, and then deposited in the chamber for 10 seconds was purged.

Subsequently, the precursor compound was put in a canister and introduced into the deposition chamber through a vapor flow controller (VFC) as shown in Table 1, and the chamber was purged for 10 seconds.

Next, the concentration of O ₃ in O ₂ as a reactive gas was set to 200 g/m ³ , and was introduced into the deposition chamber as shown in Table 1, and the chamber was purged for 10 seconds. At this time, the substrate on which the thin film was to be formed was heated under the temperature conditions shown in Table 1 below.

This process was repeated 100 to 400 times to form a self-limiting atomic layer thin film having a thickness of 10 nm.

For each thin film of Examples 1 to 7 and Comparative Examples 1 to 10 obtained, the deposition rate reduction rate (D/R reduction rate) and SIMS C impurity were measured in the following manner and are shown in Table 1 below.

^* Deposition rate reduction rate (D/R (dep. rate) reduction rate): This refers to the rate at which the deposition rate is reduced after the shield is added compared to the D/R before the oxide film reaction surface control agent is added. was calculated as

Specifically, the thickness of the thin film measured with an ellipsometer, which is a device that can measure optical properties such as thickness or refractive index of the thin film using the polarization characteristics of light for the manufactured thin film, is divided by the number of cycles to obtain 1 cycle The thin film growth rate reduction rate was calculated by calculating the thickness of the thin film deposited per layer. Specifically, it was calculated using Equation 1 below.

[Equation 1]

Deposition rate reduction rate = [{(DR _i )-(DR _f )}/(DR _i )]×100

(In the above formula, DR (Deposition rate, Å/cycle) is the rate at which a thin film is deposited. In thin film deposition formed of precursors and reactants, DR _i (initial deposition rate) is the rate of thin film formed without introducing a reactive surface control agent. Deposition rate DR _f (final deposition rate) is the deposition rate of the thin film formed by injecting the oxide film reaction surface control agent during the above process, where the deposition rate (DR) is 3 to 30 nm using an ellipsometer The thickness of the thin film is measured at room temperature and normal pressure, and the unit of Å/cycle is used.)

* For non-uniformity, the results calculated using Equation 2 below after selecting the highest thickness and minimum thickness among the thicknesses of the thin film measured by the ellipsometer equipment are shown in Table 1 below. Specifically, the thicknesses of four edge portions and one central portion of a 300 mm wafer were measured respectively.

[Equation 2]

Non-uniformity% = [{(maximum thickness-minimum thickness)/2}×average thickness]×100

^* SIMS (Secondary-ion mass spectrometry) C impurity: When ion sputter penetrates the thin film in the axial direction and the sputter time is 50 seconds with little contamination on the surface layer of the substrate, the C impurity value is calculated in the SIMS graph by considering the C impurity content (counts). Confirmed.

* Step coverage (%): 100 nm from top to bottom (left drawing) and 100 nm from bottom to top of thin films deposited by Examples 1 to 7 and Comparative Examples 1 to 10 on a substrate having a complex structure with an aspect ratio of 22:1 The position (right drawing) was calculated according to Equation 3 by measuring the TEM of the specimen horizontally cut.

[Equation 3]

Step coverage (%) = (Thickness deposited on the lower inner wall / Thickness deposited on the upper inner wall) × 100

Specifically, a deposition process was performed using a diffusion improving material application condition on a substrate having a complex structure with an aspect ratio of 22:1 having an upper diameter of 90 nm, a lower diameter of 65 nm, and a via hole depth of about 2000 nm, and then the thickness uniformity and thickness deposited inside the vertically formed via hole To check the step coverage, specimens were prepared by horizontally cutting 100 nm from the top to the bottom and 100 nm from the bottom to the top, measured using a transmission electron microscope (TEM), and are shown in Table 1 and Figures 2 and 3 below.

No. precursor reactive gas Oxide film reaction surface control agent (chemical formula No.) deposition temperature Precursor injection conditions Reaction gas injection condition Oxide film reaction surface control agent injection conditions deposition rate
(Å/cycle) non-uniformity
(%) Equation 1 Calculation SIMS C Analysis (counts/s) step coverage
(22:1 S/C)
(%) Comparative Example 1 CpHf O ₃ - 420℃ VFC, 3s, 100 sccm 5s, 500sccm - 0.93 1.22 - 428.9 23.6 Comparative Example 2 CpHf O ₃ Tetrahydrofuran 400℃ VFC, 3s, 100 sccm 5s, 500sccm 30mg/cycle 0.85 3.87 9% 524.3 75.6 Comparative Example 3 CpHf O ₃ Cyclopentyl methyl ether 400℃ VFC, 3s, 100 sccm 5s, 500sccm 30mg/cycle 0.79 4.14 15% 537.5 70.7 Comparative Example 4 CpHf O ₃ Trimethyl orthoacetate 400℃ VFC, 3s, 100 sccm 5s, 500sccm 30mg/cycle 0.58 23.82 37% 600.9 84.9 Comparative Example 5 CpHf O ₃ Monoglyme 400℃ VFC, 3s, 100 sccm 5s, 500sccm 30mg/cycle 0.67 6.84 28% 583.7 N/A Comparative Example 6 CpHf O ₃ Methyl propionate 400℃ VFC, 3s, 100 sccm 5s, 500sccm 30mg/cycle 0.83 9.53 11% 1008.5 87.3 Comparative Example 7 CpHf O ₃ γ-Valerolactone 400℃ VFC, 3s, 100 sccm 5s, 500sccm 30mg/cycle 0.84 3.42 9% 708.5 N/A Comparative Example 8 CpHf O ₃ Acetone 400℃ VFC, 3s, 100 sccm 5s, 500sccm 30mg/cycle 0.79 6.63 15% 753.4 73.2 Comparative Example 9 CpHf O ₃ Acetylacetone 400℃ VFC, 3s, 100 sccm 5s, 500sccm 30mg/cycle 0.58 11.06 38% 935.6 N/A Example 1 CpHf O ₃ Formula 2-1 420℃ VFC, 3s, 100 sccm 5s, 500sccm 15 mg/cycle 0.10 2.51 89% 387.9 110.5 Example 2 CpHf O ₃ Formula 2-2 400℃ VFC, 3s, 100 sccm 5s, 500sccm 20mg/cycle 0.21 2.08 77% 393.7 N/A Example 3 CpHf O ₃ Formula 2-3 400℃ VFC, 3s, 100 sccm 5s, 500sccm 10 mg/cycle 0.32 1.90 66% 329.6 94.1 Example 4 CpHf O ₃ Formula 1-3 400℃ VFC, 3s, 100 sccm 5s, 500sccm 15 mg/cycle 0.37 3.60 60% 408.8 N/A Comparative Example 10 TMA O3 Al2O3 400℃ VFC, 2s, 100 sccm 5s, 300sccm - 0.75 1.20 - 73.2 95.0 Example 5 TMA O3 Formula 2-1 400℃ VFC, 2s, 100 sccm 5s, 300sccm 15 mg/cycle 0.26 2.86 65% 54.1 101.0 Example 6 TMA O3 Formula 2-2 400℃ VFC, 2s, 100 sccm 5s, 300sccm 25mg/cycle 0.30 2.90 60% 53.8 100.0 Example 7 TMA O3 Formula 2-3 400℃ VFC, 2s, 100 sccm 5s, 300sccm 20mg/cycle 0.35 3.73 53% 56.8 98.0

In the above table, CpHf is an abbreviation of Tris(dimethylamido)cyclopentadienyl hafnium, and TMA is an abbreviation of trimethyl aluminum.

As shown in Table 1, Examples 1 to 7 using the oxide film reaction surface control agent and the precursor compound according to the present invention not only significantly improved the deposition rate reduction rate compared to Comparative Example 1 without using the same, but also improved the impurity reduction characteristics and It was confirmed that the step coverage was excellent.

In addition, in Examples 1 to 7 using the oxide film reaction surface control agent according to the present invention, the deposition rate reduction rate was significantly improved compared to Comparative Examples 2 to 10 using other types out of the suitable type, as well as impurity reduction characteristics and step coverage. I was able to confirm this excellence.

Specifically, the deposition rate reduction rate confirmed through the difference between the growth rates of Comparative Examples 2 to 10 without using the oxide film reaction surface control agent according to the present invention was 9 to 38%, whereas the oxide film reaction surface control agent according to the present invention In Examples 1 to 7 used, it was confirmed that the deposition rate reduction rate, which was confirmed through the difference between the growth rates, was excellent at 53 to 89%.

Through this, it is expected that effective step coverage is realized even on a pattern substrate having a high aspect ratio.

In fact, as shown in FIGS. 2 and 3 below, the step coverage measured according to Comparative Examples 2, 3, 4, 6, 8, and 10 was 23.6% or more and up to 95%, whereas Example 1 according to the present invention , 3, 5, 6, and 7, it was confirmed that the step coverage was excellent at a minimum of 94.1% and a maximum of 110.5%, thereby providing increased thickness on both the upper and lower portions when the oxide film reaction surface control agent was used according to the present invention. could

Claims (15)

A trivalent metal, a tetravalent metal, a pentavalent metal or An oxide film reaction surface control agent characterized in that it controls the reaction surface of an oxide film formed from at least one precursor compound selected from hexavalent metals. According to claim 1,
The unshared electron pair is an oxide film reaction surface control agent, characterized in that at least one selected from oxygen (O), sulfur (S), phosphorus (P), and nitrogen (N). According to claim 1,
The oxide film reaction surface control agent, characterized in that the cyclic compound having three or more elemental species having unshared electron pairs is a compound represented by the following formula (1).
[Formula 1]

(In Formula 1, R' is 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 A is oxygen (O), sulfur (S), Phosphorus (P) or nitrogen (N), wherein m is an integer from 0 to 2.) According to claim 1,
The oxide film reaction surface control agent, characterized in that the linear compound having three or more elemental species having unshared electron pairs is a compound represented by the following formula (2).
[Formula 2]

(In Formula 2, R ^” is 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,
B is -OH, -OCH ₃ , -OCH ₂ CH ₃ , -CH ₂ CH ₃ , -SH, -SCH ₃ , or -SCH ₂ CH ₃ .) According to claim 1,
The oxide film reaction surface control agent, characterized in that the refractive index of 1.365 to 1.48. According to claim 1,
The metals are Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re An oxide film reaction surface control agent characterized in that it controls the reaction surface of an oxide film formed from one or more precursor compounds selected from the group consisting of Os, Ir, La, Ce and Nd. According to claim 1,
The oxide film reaction surface control agent characterized in that it comprises at least one compound selected from the compounds represented by the following formulas 1-1 to 1-3 and formulas 2-1 to 2-3.
[Formula 1-1 to 1-3]
, ,
[Formula 2-1 to 2-3]
, , Treating the surface of the substrate with the oxide film reaction surface control agent according to any one of claims 1 to 7; and
Forming an oxide film on the surface of the loaded substrate by sequentially injecting a precursor compound and a reactive gas into a chamber on the treated substrate. According to claim 8,
The method of forming an oxide film, characterized in that the chamber is an ALD chamber, a CVD chamber, a PEALD chamber or a PECVD chamber. According to claim 8,
The substrate surface treatment step is an oxide film formation method, characterized in that carried out by applying the oxide film reaction surface control agent to the substrate loaded in the chamber at 20 to 800 ° C. According to claim 8,
The oxide film formation method, characterized in that the oxide film reaction surface control agent and the precursor compound are transferred into the chamber by a VFC method, a DLI method or an LDS method. According to claim 8,
The oxide film forming method according to claim 1 , wherein the oxide film is a silicon oxide film, a titanium oxide film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, an aluminum oxide film, a niobium oxide film, or a thallium oxide film. A semiconductor substrate comprising an oxide film produced by the method of forming an oxide film according to claim 8 . According to claim 13,
The semiconductor substrate, characterized in that the oxide film has a multilayer structure of two or three layers or more. A semiconductor device comprising the semiconductor substrate of claim 13 .