Growth inhibitor for film formation, film formation method using the same, and semiconductor substrate manufactured thereby

Abstract

The present application relates to a growth inhibitor for film formation, a film formation method using the same, and a semiconductor substrate manufactured thereby. Specifically, it relates to a growth inhibitor for film formation which is a compound represented by Chemical Formula 1, a film formation method using the same, and a semiconductor substrate manufactured thereby, [Chemical Formula 1] AnB m X o Y i Z j wherein A is carbon or silicon; B is hydrogen or an alkyl group having 1 to 3 carbon atoms; X is one or more selected from fluorine, chlorine, bromine, and iodine; Y and Z are each independently one or more selected from oxygen, nitrogen, sulfur, and fluorine, and are different from each other; n is an integer of 1 to 15; o is an integer of 1 or more; m is 0 to 2n+1; i and j are each an integer of 0 to 3. The present application can suppress side reactions, reduce film growth rate, and remove process by-products in the film, thereby greatly improving step coverage and thickness uniformity of the film even when forming a film on a substrate having a complex structure.

Description

Technical Field

[0001] This invention relates to a growth inhibitor for thin film formation, a thin film formation method using the same, and a semiconductor substrate manufactured therefrom. Specifically, it relates to a growth inhibitor for thin film formation capable of suppressing side reactions to appropriately reduce the thin film growth rate and remove process byproducts within the thin film, thereby preventing corrosion or degradation. Even when forming thin films on substrates with complex structures, it can significantly improve step coverage and thin film thickness uniformity. Background Technology

[0002] As the integration of memory and non-memory semiconductor devices increases and their structures become more complex, step coverage becomes increasingly important when depositing various thin films onto substrates.

[0003] The semiconductor thin film is formed from metal nitrides, metal oxides, metal silicides, etc. The metal nitride thin films include titanium nitride (TiN), tantalum nitride (TaN), zirconium nitride (ZrN), etc. These films are typically used as silicon layers for doped semiconductors and as diffusion barriers for aluminum (Al), copper (Cu), etc., used as interlayer wiring materials. However, tungsten (W) thin films are used as adhesion layers when deposited onto the substrate.

[0004] To achieve excellent and uniform physical properties in the thin film deposited on the substrate, high step coverage is essential. Therefore, atomic layer deposition (ALD), which utilizes surface reactions, is increasingly used compared to chemical vapor deposition (CVD), which primarily utilizes vapor-phase reactions. However, achieving 100% step coverage remains a challenge.

[0005] In addition, when titanium tetrachloride (TiCl4) is used to deposit titanium nitride (TiN), a representative metal nitride, the prepared film will contain residual process byproducts such as chlorides, which can induce corrosion of metals such as aluminum and generate non-volatile byproducts, leading to film degradation.

[0006] Therefore, there is a need to develop methods for forming thin films with complex structures without corroding interlayer wiring materials, as well as semiconductor substrates manufactured thereby.

[0007] Prior art literature

[0008] Patent documents

[0009] Korean Patent Publication No. 2006-0037241 Summary of the Invention

[0010] Technical issues

[0011] In order to solve the problems existing in the prior art as described above, the object of the present invention is to provide a growth inhibitor for thin film formation, a thin film formation method using the same, and a semiconductor substrate manufactured therefrom. The growth inhibitor for thin film formation can suppress side reactions to appropriately reduce the thin film growth rate and remove process by-products in the thin film, thereby preventing corrosion or deterioration. Even when forming a thin film on a substrate with a complex structure, it can significantly improve step coverage and thin film thickness uniformity.

[0012] The purpose of this invention is to improve the crystallinity of thin films, thereby improving the density and electrical properties of the thin films.

[0013] All of the above-mentioned and other objectives of the present invention can be achieved by the present invention as described below.

[0014] Technical solution

[0015] To achieve the above objectives, the present invention provides a growth inhibitor for thin film formation, wherein the growth inhibitor for thin film formation is a compound represented by chemical formula 1.

[0016] [Chemical Formula 1]

[0017] A n B m X o Y i Z j

[0018] Wherein, A is carbon or silicon; B is hydrogen or an alkyl group having 1 to 3 carbon atoms; X is one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); Y and Z are each independently selected from one or more of oxygen, nitrogen, sulfur, and fluorine and are different from each other; n is an integer from 1 to 15; o is an integer greater than or equal to 1; m is from 0 to 2n+1; and i and j are integers from 0 to 3.

[0019] In addition, the growth inhibitor for thin film formation of the present invention can be used as a film modifier.

[0020] In addition, the present invention provides a thin film formation method, which includes the following steps: injecting the growth inhibitor for thin film formation into an ALD chamber and adsorbing it onto the surface of the loaded substrate.

[0021] In addition, the present invention provides a semiconductor substrate, which is manufactured by the thin film forming method.

[0022] Beneficial effects

[0023] According to the present invention, a growth inhibitor for thin film formation, a thin film formation method thereunder, and a semiconductor substrate therefrom can be provided. The growth inhibitor for thin film formation can suppress side reactions and reduce the deposition rate to appropriately reduce the thin film growth rate and remove process byproducts in the thin film, thereby preventing corrosion or deterioration. Even when forming a thin film on a substrate with a complex structure, it can significantly improve step coverage and the thickness uniformity of the thin film.

[0024] This invention can improve the crystallinity of thin films, thereby improving the density and electrical properties of the thin films. Attached Figure Description

[0025] Figure 1 It is a process diagram used to illustrate the existing ALD process.

[0026] Figure 2 This is a process diagram illustrating an embodiment of the ALD process of the present invention.

[0027] Figure 3 , Figure 4 This is a SIMS analysis graph showing the reduction rate of Cl element and the like based on deposition temperature for Example 1 (SP-TiCl4) and Comparative Example 1 (TiCl4) of the present invention.

[0028] Figure 5 These are TEM images of cross-sections near the top and bottom of the TiN thin films formed in Example 1 (SP-TiCl4) and Comparative Example 1 (TiCl4) of the present invention.

[0029] Figure 6 Is for Figure 5 An illustration of the cross-sectional positions of the top and bottom sections.

[0030] Figure 7 These are SIMS analysis diagrams of the SiN thin films prepared in Example 5 and Comparative Example 4.

[0031] Figure 8 The XRD patterns are for Comparative Example 1 (without the addition of a growth inhibitor for thin film formation (Ref TiN)), Example 4 (with the addition of a growth inhibitor for thin film formation (tert-BuI (0.1 g / min)) at a rate of 0.1 g / min), and Example 4 (with the addition of a growth inhibitor for thin film formation (tert-BuI (0.01 g / min)) at a rate of 0.01 g / min).

[0032] Figure 9 This is a SIMS analysis graph showing the reduction rate of elements such as F (fluorine) and C (carbon) based on deposition time for Example 6 (SP-NbF5) and Comparative Example 5 (NbF5) of the present invention. The right graph shows the thin film forming growth inhibitor used in this invention, while the left graph shows Comparative Example 5 as a reference, without the use of the thin film forming growth inhibitor. Detailed Implementation

[0033] The following describes in detail the growth inhibitor for thin film formation, the thin film formation method using the same, and the semiconductor substrate manufactured therefrom.

[0034] The inventors of this invention have confirmed that when a halogenated compound with a predetermined structure is adsorbed as a thin film growth inhibitor before the thin film precursor compound is adsorbed onto the surface of a substrate loaded into an ALD chamber, the growth rate of the film formed after deposition is significantly reduced, thus significantly improving step coverage and greatly reducing the amount of halide residues as process byproducts. Furthermore, it has been confirmed that when the thin film precursor compound is first adsorbed onto the surface of a substrate loaded into an ALD chamber, and then a halogenated compound with a predetermined structure is adsorbed as a thin film growth inhibitor, it unexpectedly acts as a film quality modifier, increasing the film growth rate, significantly reducing the amount of halide residues as process byproducts, and significantly improving the film density, resistivity, etc. Based on these results, further research was conducted, and this invention was completed.

[0035] The growth inhibitor for thin film formation of the present invention is a compound represented by chemical formula 1.

[0036] [Chemical Formula 1]

[0037] A n B m X o Y i Z j

[0038] Wherein, A is carbon or silicon; B is hydrogen or an alkyl group having 1 to 3 carbon atoms; X is one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); Y and Z are each independently selected from one or more of oxygen, nitrogen, sulfur, and fluorine and are different from each other; n is an integer from 1 to 15; o is an integer greater than 1; m is 0 to 2n+1; i and j are integers from 0 to 3. In this case, side reactions can be suppressed during film formation to reduce film growth rate and remove process by-products within the film, thereby reducing corrosion or degradation. Even when forming films on substrates with complex structures, step coverage and film thickness uniformity can be significantly improved.

[0039] The B is preferably hydrogen or methyl, and the n is preferably an integer from 2 to 15, more preferably an integer from 2 to 10, even more preferably an integer from 2 to 6, and even more preferably an integer from 4 to 6. Within this range, the removal effect of process by-products is significant and the step coverage is excellent.

[0040] In the chemical formula 1, X is preferably one or more of bromine (Br) and iodine (I), more preferably iodine, which has the effect of suppressing side reactions and removing process by-products more effectively.

[0041] In the chemical formula 1, o is preferably an integer from 1 to 5, more preferably an integer from 1 to 3, and even more preferably 1 or 2. Within this range, the reduction in deposition rate is significant, thereby having the advantage of more effectively improving step coverage.

[0042] The m is preferably 1 to 2n+1, more preferably 3 to 2n+1. Within this range, the removal effect of process by-products is significant and the step coverage is excellent.

[0043] Preferably, Y and Z are each independently selected from one or more of oxygen, nitrogen, and fluorine, and are different from each other.

[0044] Preferably, neither i nor j is 0; specifically, they can be integers from 1 to 3.

[0045] The compound represented by Formula 1 is preferably a branched, cyclic, or aromatic compound, specifically selected from tert-butyl bromide, 1-methyl-1-bromocyclohexane, 1-iodopropane, 1-iodobutane, 1-iodo-2-methylpropane, 1-iodo-1-isopropylcyclohexane, 1-iodo-4-nitrobenzene, 1-iodo-4-methoxybenzene, 1-iodo-2-methylpentane, 1-iodo-4-trifuloromethylbenzene, and tert-butyl iodide. In this case, the removal of process byproducts is significantly improved, and the improvement in step coverage and membrane quality is excellent.

[0046] Preferably, the compound represented by the chemical formula 1 is used in the atomic layer deposition (ALD) process. In this case, it has the advantage that it not only does not hinder the adsorption of the thin film precursor compound, but also acts as a growth inhibitor to effectively protect the surface of the substrate and effectively remove process byproducts.

[0047] Preferably, the compound represented by chemical formula 1 is a liquid at room temperature (22°C) with a density of 0.8–2.5 g / cm³. 3 Or 0.8~1.5g / cm 3The vapor pressure (20℃) is 0.1~300mmHg or 1~300mmHg, and the solubility in water (25℃) is below 200mg / L. Within this range, it has excellent effects on step coverage, film thickness uniformity and film quality improvement.

[0048] More preferably, the density of the compound represented by chemical formula 1 is 0.85–2.0 g / cm³. 3 Or 0.85~1.3g / cm 3 The vapor pressure (20℃) is 1~260mmHg, and the solubility in water (25℃) is below 160mg / L. Within this range, it has excellent effects on step coverage, film thickness uniformity and film quality improvement.

[0049] The thin film formation method of the present invention includes the following steps: injecting a thin film formation growth inhibitor represented by chemical formula 1 into an ALD chamber and allowing it to adsorb onto the surface of a loaded substrate.

[0050] [Chemical Formula 1]

[0051] A n B m X o Y i Z j

[0052] Wherein, A is carbon or silicon; B is hydrogen or an alkyl group having 1 to 3 carbon atoms; X is one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); Y and Z are each independently selected from one or more of oxygen, nitrogen, sulfur, and fluorine and are different from each other; n is an integer from 1 to 15; o is an integer greater than 1; m is 0 to 2n+1; i and j are integers from 0 to 3. In this case, side reactions can be suppressed and the deposition rate slowed down to reduce the film growth rate and remove process by-products in the film, thereby significantly improving step coverage and film thickness uniformity even when forming films on substrates with complex structures.

[0053] In the step of adsorbing the growth inhibitor for thin film formation onto the substrate surface, the feeding time for supplying the growth inhibitor for thin film formation to the substrate surface per cycle is preferably 1 to 10 seconds, more preferably 1 to 5 seconds, even more preferably 2 to 5 seconds, and even more preferably 2 to 4 seconds. Within this range, it has the advantages of low thin film growth rate, good step coverage, and excellent economy.

[0054] In this invention, the feeding time of the growth inhibitor for film formation is based on a chamber volume of 15 to 20 L and a flow rate of 0.5 to 5 mg / s, and more specifically, on a chamber volume of 18 L and a flow rate of 1 to 2 mg / s.

[0055] In a preferred embodiment, the thin film formation method may include the following steps: step i), vaporizing the growth inhibitor for thin film formation and adsorbing it onto the surface of the substrate loaded into the ALD chamber; step ii), performing a first purging of the ALD chamber using a purge gas; step iii), vaporizing the thin film precursor compound and adsorbing it onto the surface of the substrate loaded into the ALD chamber; step iv), performing a second purging of the ALD chamber using a purge gas; step v), supplying a reactant gas into the ALD chamber; and step vi), performing a third purging of the ALD chamber using a purge gas. The advantage of this method is that the thin film growth rate is appropriately reduced, and even if the deposition temperature is increased during thin film formation, the generated process byproducts can be effectively removed, thereby reducing the resistivity of the thin film and significantly improving step coverage.

[0056] In another preferred embodiment, the thin film formation method may include the following steps: step i), vaporizing a thin film precursor compound and adsorbing it onto the surface of a substrate loaded into an ALD chamber; step ii), performing a first purging of the ALD chamber using a purge gas; step iii), vaporizing a growth inhibitor for thin film formation and adsorbing it onto the surface of a substrate loaded into an ALD chamber; step iv), performing a second purging of the ALD chamber using a purge gas; step v), supplying a reaction gas into the ALD chamber; and step vi), performing a third purging of the ALD chamber using a purge gas. The advantage of this method is that the thin film growth rate is increased, and even with increased deposition temperature during thin film formation, the generated process byproducts can be effectively removed, thereby reducing the resistivity of the thin film and significantly increasing its density and crystallinity.

[0057] The growth inhibitor and precursor compound for thin film formation are preferably transferred into the ALD chamber via gas flow control (VFC), direct liquid injection (DLI), or liquid transfer system (LDS), and more preferably transferred into the ALD chamber via LDS.

[0058] The ratio of the growth inhibitor for film formation to the amount of the film precursor compound added in the ALD chamber (mg / cycle) is 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 reduction rate of film growth rate (GPC) per cycle is high, and the reduction effect of process by-products is significant.

[0059] The thin film precursor compound is not particularly limited, as long as it is a thin film precursor compound commonly used in ALD (atomic layer deposition) methods, but preferably a metal film precursor compound, a metal oxide film precursor compound, a metal nitride film precursor compound, or a silicon nitride film precursor compound. Preferably, the metal includes one or more selected from tungsten, cobalt, chromium, aluminum, hafnium, vanadium, niobium, germanium, lanthanides, actinides, gallium, tantalum, zirconium, ruthenium, copper, titanium, nickel, iridium, and molybdenum.

[0060] As an example, the thin film precursor compound containing niobium in the metal is preferably NbF5, which has the advantage of well exhibiting the effects expected by the present invention.

[0061] As an example, the metal film precursor, metal oxide film precursor, and metal nitride film precursor may be selected from one or more of metal halides, metal alkoxides, alkyl metal compounds, metal amino compounds, metal carbonyl compounds, and substituted or unsubstituted cyclopentadienyl metal compounds, but are not limited thereto.

[0062] Specifically, the metal film precursor, metal oxide film precursor, and metal nitride film precursor can be selected from titanium tetrachloride, germanium tetrachloride, tin tetrachloride, tris(isopropyl)ethylmethylaminogermanium, tetraethoxygermanium, tetramethyltin, tetraethyltin, bis(acetylacetonate)tin, trimethylaluminum, tetrakis(dimethylamino)germanium, bis(n-butylamino)germanium, tetrakis(ethylmethylamino)tin, tetrakis(dimethylamino)tin, and Co2(CO)8(dicobalt). The following are some of the following, but not limited to: octacarbonyl (cobalt octacarbonyl), Cp2Co (biscyclopentadienylcobalt), Co(CO)3(NO) (cobalt tricarbonyl nitrosyl), and CpCo(CO)2 (cabalt dicarbonyl cyclopentadienyl).

[0063] As an example, the silicon nitride film precursor may be selected from SiH4, SiCl4, SiF4, SiCl2H2, Si2Cl6, TEOS, DIPAS, BTBAS, (NH2)Si(NHMe)3, (NH2)Si(NHEt)3, (NH2)Si(NH n Pr)3、(NH2)Si(NH i Pr)3、(NH2)Si(NH n Bu)3、(NH2)Si(NH i Bu)3、(NH2)Si(NH t Bu)3, (NMe2)Si(NHMe)3, (NMe2)Si(NHEt)3, (NMe2)Si(NH n Pr)3、(NMe2)Si(NH iPr)3、(NMe2)Si(NH n Bu)3、(NMe2)Si(NH i Bu)3、(NMe2)Si(NH t Bu)3、(NEt2)Si(NHMe)3、(NEt2)Si(NHEt)3、(NEt2)Si(NH n Pr)3、(NEt2)Si(NH i Pr)3、(NEt2)Si(NH n Bu)3、(NEt2)Si(NH i Bu)3、(NEt2)Si(NH t Bu)3, (N n Pr2)Si(NHMe)3、(N n Pr2)Si(NHEt)3、(N n Pr2)Si(NH n Pr)3, (N n Pr2)Si(NH i Pr)3, (N n Pr2)Si(NH n Bu)3, (N n Pr2)Si(NH i Bu)3, (N n Pr2)Si(NH t Bu)3, (N i Pr2)Si(NHMe)3、(N i Pr2)Si(NHEt)3、(N i Pr2)Si(NH n Pr)3, (N i Pr2)Si(NH i Pr)3, (N i Pr2)Si(NH n Bu)3, (N i Pr2)Si(NH i Bu)3, (N i Pr2)Si(NH t Bu)3, (N n Bu2)Si(NHMe)3、(N n Bu2)Si(NHET)3、(N n Bu2)Si(NH n Pr)3, (N n Bu2)Si(NH i Pr)3, (N n Bu2)Si(NH n Bu)3, (Nn Bu2)Si(NH i Bu)3, (N n Bu2)Si(NH t Bu)3, (N i Bu2)Si(NHMe)3、(N i Bu2)Si(NHET)3、(N i Bu2)Si(NH n Pr)3, (N i Bu2)Si(NH i Pr)3, (N i Bu2)Si(NH n Bu)3, (N i Bu2)Si(NH i Bu)3, (N i Bu2)Si(NH t Bu)3, (N t Bu2)Si(NHMe)3、(N t Bu2)Si(NHET)3、(N t Bu2)Si(NH n Pr)3, (N t Bu2)Si(NH i Pr)3, (N t Bu2)Si(NH n Bu)3, (N t Bu2)Si(NH i Bu)3, (N t Bu2)Si(NH t Bu)3, (NH2)2Si(NHMe)2, (NH2)2Si(NHEt)2, (NH2)2Si(NH n Pr)2、(NH2)2Si(NH i Pr)2、(NH2)2Si(NH n Bu)2、(NH2)2Si(NH i Bu)2、(NH2)2Si(NH t Bu)2、(NMe2)2Si(NHMe)2、(NMe2)2Si(NHEt)2、(NMe2)2Si(NH n Pr)2、(NMe2)2Si(NH i Pr)2、(NMe2)2Si(NH n Bu)2、(NMe2)2Si(NH i Bu)2、(NMe2)2Si(NH tBu)2、(NEt2)2Si(NHMe)2、(NEt2)2Si(NHEt)2、(NEt2)2Si(NH n Pr)2、(NEt2)2Si(NH i Pr)2、(NEt2)2Si(NH n Bu)2、(NEt2)2Si(NH i Bu)2、(NEt2)2Si(NH t Bu)2, (N n Pr2)2Si(NHMe)2、(N n Pr2)2Si(NHEt)2、(N n Pr2)2Si(NH n Pr)2、(N n Pr2)2Si(NH i Pr)2、(N n Pr2)2Si(NH n Bu)2, (N n Pr2)2Si(NH i Bu)2, (N n Pr2)2Si(NH t Bu)2, (N i Pr2)2Si(NHMe)2、(N i Pr2)2Si(NHEt)2、(N i Pr2)2Si(NH n Pr)2、(N i Pr2)2Si(NH i Pr)2、(N i Pr2)2Si(NH n Bu)2, (N i Pr2)2Si(NH i Bu)2, (N i Pr2)2Si(NH t Bu)2, (N n Bu2)2Si(NHMe)2、(N n Bu2)2Si(NHEt)2、(N n Bu2)2Si(NH n Pr)2、(N n Bu2)2Si(NH i Pr)2、(N n Bu2)2Si(NH n Bu)2, (N n Bu2)2Si(NH i Bu)2, (N n Bu2)2Si(NHt Bu)2, (N i Bu2)2Si(NHMe)2、(N i Bu2)2Si(NHEt)2、(N i Bu2)2Si(NH n Pr)2、(N i Bu2)2Si(NH i Pr)2、(N i Bu2)2Si(NH n Bu)2, (N i Bu2)2Si(NH i Bu)2, (N i Bu2)2Si(NH t Bu)2, (N t Bu2)2Si(NHMe)2、(N t Bu2)2Si(NHEt)2、(N t Bu2)2Si(NH n Pr)2、(N t Bu2)2Si(NH i Pr)2、(N t Bu2)2Si(NH n Bu)2, (N t Bu2)2Si(NH i Bu)2, (N t Bu2)2Si(NH t Bu)2、Si(HNCH2CH2NH)2、Si(MeNCH2CH2NMe)2、Si(EtNCH2CH2NEt)2、Si( n PrNCH2CH2N n Pr)2、Si( i PrNCH2CH2N i Pr)2、Si( n BuNCH2CH2N n Bu)2、Si( i BuNCH2CH2N i Bu)2、Si( t BuNCH2CH2N t Bu)2、Si(HNCHCHNH)2、Si(MeNCHCHNMe)2、Si(EtNCHCHNEt)2、Si( n PrNCHCHN n Pr)2、Si( i PrNCHCHN i Pr)2、Si( n BuNCHCHNn Bu)2、Si( i This is it. i Bu)2、Si( t This is it. t Bu)2、(HNCHCHNH)Si(HNCH2CH2NH)、(MeNCHCHNMe)Si(MeNCH2CH2NMe)、(EtNCHCHNEt)Si(EtNCH2CH2NEt)、( n PrNCHCHN n Pr)Si( n PrNCH2CH2N n Pr)、( i PrNCHCHN i Pr)Si( i PrNCH2CH2N i Pr)、( n This is it. n Bu(Si( n This is CH2CH2N. n This)、( i This is it. i Bu(Si( i This is CH2CH2N. i This)、( t This is it. t Bu(Si( t This is CH2CH2N. t This)、(NH t Bu)2Si(HNCH2CH2NH)、(NH t Bu)2Si(MeNCH2CH2NMe)、(NH t Bu)2Si(EtNCH2CH2NEt)、(NH t This is)2Si( n PrNCH2CH2N n Pr)、(NH t This is)2Si( i PrNCH2CH2N i Pr)、(NH t This is)2Si( n This is CH2CH2N. n This)、(NH t This is)2Si( i This is CH2CH2N. i This)、(NH t This is)2Si( t This is CH2CH2N.t Bu), (NH t Bu)2Si(HNCHCHNH)、(NH t Bu)2Si(MeNCHCHNMe),(NH t Bu)2Si(EtNCHCHNEt)、(NH t Bu)2Si( n PrNCHCHN n Pr), (NH t Bu)2Si( i PrNCHCHN i Pr), (NH t Bu)2Si( n BuNCHCHN n Bu), (NH t Bu)2Si( i BuNCHCHN i Bu), (NH t Bu)2Si( t BuNCHCHN t Bu), ( i PrNCH2CH2N i Pr)Si(NHMe)2、( i PrNCH2CH2N i Pr)Si(NHET)2、( i P1NCH2CH2N i Pr)Si(NH n Pr)2、( i PrNCH2CH2N i Pr)Si(NH i Pr)2、( i PrNCH2CH2N i Pr)Si(NH n Bu)2、( i PrNCH2CH2N i Pr)Si(NH i Bu)2、( i PrNCH2CH2N i Pr)Si(NH t Bu)2、( i PrNCHCHN i Pr)Si(NHMe)2、( i PrNCHCHN i Pr)Si(NHET)2、( i PrNCHCHN i Pr)Si(NH n Pr)2、(i PrNCHCHN i Pr)Si(NH i Pr)2、( i PrNCHCHN i Pr)Si(NH n B u )2、( i PrNCHCHN i Pr)Si(NH i Bu)2 and ( i PrNCHCHN i Pr)Si(NH t One or more of Bu)2, but not limited to this.

[0064] The n P r It represents n-propyl. i Pr represents isopropyl. n Bu represents n-butyl. i Bu represents isobutyl. t Bu represents tert-butyl.

[0065] As a preferred embodiment, the thin film precursor compound may be titanium tetrahalide.

[0066] The titanium tetrahalide can be used as a metal precursor for compositions used in thin film formation. As an example, the titanium tetrahalide can be any one or more selected from TiF4, TiCl4, TiBr4, and TiI4. For example, TiCl4 is preferred in terms of economy, but it is not limited thereto.

[0067] The titanium tetrahalide exhibits excellent thermal stability, is not easily decomposed at room temperature, and is in a liquid state. Therefore, it can be used as a precursor for ALD (atomic layer deposition) to deposit thin films.

[0068] As an example, the film precursor compound can be mixed with a nonpolar solvent and then placed into the chamber. In this case, it has the advantage of being easy to adjust the viscosity or vapor pressure of the film precursor compound.

[0069] Preferably, the nonpolar solvent can be one or more selected from alkanes and cycloalkanes. In this case, it has the advantage of containing organic solvents with low reactivity and solubility and easy water management, and can improve step coverage even when the deposition temperature is increased during film formation.

[0070] More preferably, the nonpolar solvent may include C1-C10 alkanes or C3-C10 cycloalkanes, preferably C3-C10 cycloalkanes, which have the advantages of low reactivity and solubility and easy moisture management.

[0071] In this invention, C1, C3, etc. represent the number of carbon atoms.

[0072] The cycloalkanes are preferably C3 to C10 monocycloalkanes, and cyclopentane is a liquid at room temperature with the highest vapor pressure, making it a preferred choice in vapor deposition processes, but not limited thereto.

[0073] As an example, the solubility of the nonpolar solvent in water (at 25°C) can be less than 200 mg / L, preferably 50 to 200 mg / L, and more preferably 135 to 175 mg / L. Within this range, it has the advantages of low reactivity to film precursor compounds and easy moisture management.

[0074] In this invention, there are no particular limitations on solubility, as long as the measurement methods or standards conventionally used in the technical field to which this invention pertains are followed. For example, saturated solutions can be measured by HPLC.

[0075] The content of the nonpolar solvent relative to the total weight of the film precursor compound and the nonpolar solvent is preferably 5-95% by weight, more preferably 10-90% by weight, even more preferably 40-90% by weight, and most preferably 70-90% by weight.

[0076] When the content of the nonpolar solvent added exceeds the upper limit, it will induce impurities, leading to an increase in resistance and impurity values ​​within the thin film. When the content of the organic solvent added is less than the lower limit, the disadvantage is that the improvement in step coverage caused by the addition of solvent and the reduction in impurities such as chloride (Cl) ions are poor.

[0077] As an example, in the thin film formation method, the thin film growth rate per cycle calculated according to mathematical formula 1 The reduction rate is less than -5%, preferably less than -10%, more preferably less than -20%, even more preferably less than -30%, further preferably less than -40%, and most preferably less than -45%. Within this range, the step coverage and film thickness uniformity are excellent.

[0078] [Mathematical Expression 1]

[0079] Reduction in film growth rate per cycle (%) = [(Film growth rate per cycle with growth inhibitor used - Film growth rate per cycle without growth inhibitor used) / Film growth rate per cycle without growth inhibitor used] × 100

[0080] The residual halogen strength (c / s) in the film formed after 200 cycles according to the thin film forming method is preferably 10,000 or less, more preferably 8,000 or less, even more preferably 7,000 or less, and even more preferably 6,000 or less. Within this range, the effect of preventing corrosion and deterioration is excellent.

[0081] In this invention, the purging rate is preferably 1,000 to 10,000 sccm, more preferably 2,000 to 7,000 sccm, and even more preferably 2,500 to 6,000 sccm. Within this range, the film growth rate per cycle is reduced to a preferred range, and process byproducts are reduced.

[0082] The ALD (Atomic Layer Deposition) process is highly advantageous in manufacturing integrated circuits (ICs) that require high aspect ratios, especially due to its self-limiting thin film growth mechanism, which provides advantages such as excellent conformality, uniformity, and precise thickness control.

[0083] As an example, the thin film formation method can be carried out at a deposition temperature in the range of 50 to 900°C, preferably in the range of 300 to 700°C, more preferably in the range of 350 to 600°C, even more preferably in the range of 400 to 550°C, and even more preferably in the range of 400 to 500°C. Within this range, the ALD process characteristics are significantly achieved and the film with excellent quality is grown.

[0084] As an example, the thin film formation method can be carried out at a deposition pressure in the range of 0.1 to 10 Torr, preferably in the range of 0.5 to 5 Torr, and more preferably in the range of 1 to 3 Torr, within which a thin film with uniform thickness can be obtained.

[0085] In this invention, the deposition temperature and deposition pressure can be the measured temperature and pressure formed in the deposition chamber, or the measured temperature and pressure applied to the substrate in the deposition chamber.

[0086] Preferably, the thin film formation method includes the following steps: heating the temperature inside the chamber to the deposition temperature before introducing the growth inhibitor for thin film formation into the chamber; and / or injecting an inert gas into the chamber for purging before introducing the growth inhibitor for thin film formation into the chamber.

[0087] Furthermore, the present invention provides a thin film preparation apparatus capable of implementing the aforementioned thin film preparation method. The thin film preparation apparatus includes: an ALD chamber; a first vaporizer for vaporizing a growth inhibitor for thin film formation; a first transfer unit for transferring the vaporized growth inhibitor into the ALD chamber; a second vaporizer for vaporizing a Ti-based thin film precursor; and a second transfer unit for transferring the vaporized Ti-based thin film precursor into the ALD chamber. The vaporizer and transfer unit are not particularly limited, as long as they are vaporizers and transfer units commonly used in the technical field to which this invention pertains.

[0088] The thin film formation method will be illustrated with specific examples.

[0089] First, the substrate to which the thin film is to be formed is placed in a deposition chamber capable of atomic layer deposition.

[0090] The substrate can be a silicon substrate, silicon oxide, or other semiconductor substrate.

[0091] The substrate may further have a conductive layer or an insulating layer formed on its upper part.

[0092] The growth inhibitor for thin film formation and the thin film precursor compound or a mixture thereof with a nonpolar solvent are prepared separately to deposit a thin film on a substrate located in the deposition chamber.

[0093] Subsequently, after the prepared thin film formation inhibitor is injected into the vaporizer, it is converted into a vapor phase and transferred to the deposition chamber, where it is adsorbed onto the substrate. Then, the unadsorbed thin film formation inhibitor is purged.

[0094] Next, after the prepared thin film precursor compound or a mixture thereof with a nonpolar solvent is injected into the vaporizer, it is converted into a vapor phase and transferred to the deposition chamber, where it is adsorbed onto the substrate. Then, the unadsorbed thin film forming composition is purged.

[0095] In this invention, as an example, the method of transferring the thin film formation inhibitor and the thin film precursor compound into the deposition chamber can be a vapor flow control (VFC) method that uses a vapor flow control method to transfer volatile gases or a liquid delivery system (LDS) method that uses a liquid flow control method to transfer liquids, with the LDS method being preferred.

[0096] At this time, the carrier gas or dilution gas used to move the thin film forming inhibitor and thin film precursor compound onto the substrate can be one or a mixture of two or more selected from argon (Ar), nitrogen (N2), and helium (He), but is not limited thereto.

[0097] In this invention, as an example, the purging gas can be an inert gas, preferably the carrier gas or dilution gas described above.

[0098] Next, a reaction gas is supplied. The reaction gas is not particularly limited, as long as it is a reaction gas conventionally used in the technical field to which this invention pertains, preferably including a reducing agent, a nitriding agent, or an oxidizing agent. The reducing agent reacts with the thin film precursor compound adsorbed on the substrate to form a metal thin film, the nitriding agent forms a metal nitride thin film, and the oxidizing agent forms a metal oxide thin film.

[0099] Preferably, the reducing agent can be ammonia (NH3) or hydrogen (H2), the nitriding agent can be nitrogen (N2), and the oxidizing agent can be one or more selected from H2O, H2O2, O2, O3, and N2O.

[0100] The next step is to purge the unreacted residual reaction gases using an inert gas. This not only removes excess reaction gases but also removes the generated byproducts.

[0101] As described above, the steps of adsorbing the thin film forming inhibitor onto the substrate, purging the unadsorbed thin film forming inhibitor, adsorbing the thin film precursor compound onto the substrate, purging the unadsorbed thin film forming composition, supplying the reactive gas, and purging the residual reactive gas can be used as a unit cycle, and the unit cycle can be repeated to form a thin film of the desired thickness.

[0102] As an example, the unit cycle can be 100 to 1000 times, preferably 100 to 500 times, and more preferably 150 to 300 times. Within this range, it has a good effect of exhibiting the characteristics of the target thin film.

[0103] Figure 1 It is a process diagram used to illustrate the existing ALD process. Figure 2 This is a process diagram illustrating an embodiment of the ALD process of the present invention. (Refer to...) Figure 1 As with existing ALD processes, when the growth inhibitor for film formation of this invention is not adsorbed before the adsorption of the film precursor compound (e.g., TiCl4) to protect the substrate surface, process byproducts such as HCl remain in the film (e.g., TiN) formed by reacting with the reaction gas (e.g., NH3), leading to corrosion or degradation and thus reducing the substrate performance. However, as Figure 2 As shown, when the growth inhibitor (TSI) of the present invention is adsorbed before the adsorption of the film precursor compound (e.g., TiCl4) for substrate surface protection (SP), process byproducts such as HCl generated during the reaction with the reaction gas (e.g., NH3) during film formation (e.g., TiN) are removed together with the growth inhibitor, preventing corrosion or deterioration of the substrate, thereby appropriately reducing the film growth rate per cycle to improve step coverage and film thickness uniformity.

[0104] The semiconductor substrate of the present invention is manufactured by the thin film formation method of the present invention. At this time, side reactions can be suppressed to appropriately reduce the thin film growth rate and remove process by-products in the thin film, thereby achieving excellent effects in preventing corrosion or deterioration, as well as excellent step coverage and thin film thickness uniformity.

[0105] Preferably, the prepared film has a thickness of less than 20 nm, a resistivity of 0.1 to 400 μΩ·cm, a halogen content of less than 10,000 ppm, and a step coverage of more than 90%. Within this range, it performs well as an anti-diffusion film and has the effect of reducing corrosion of metal wiring materials, but is not limited thereto.

[0106] As an example, the thickness of the film is 5-20 nm, preferably 10-20 nm, more preferably 15-18.5 nm, and even more preferably 17-18.5 nm. Within this range, the film exhibits excellent film properties.

[0107] As an example, the resistivity of the thin film can be 0.1 to 400 μΩ·cm, preferably 50 to 400 μΩ·cm, and more preferably 100 to 300 μΩ·cm. Within this range, it has excellent thin film properties.

[0108] The halogen content of the film is preferably below 9,000 ppm or 1 to 9,000 ppm, more preferably below 8,500 ppm or 100 to 8,500 ppm, and even more preferably below 8,200 ppm or 1,000 to 8,200 ppm. Within this range, the film exhibits excellent film properties and reduces corrosion of metal wiring materials.

[0109] As an example, the step coverage of the thin film is 80% or more, preferably 90% or more, and more preferably 92% or more. Within this range, the advantage is that even if the thin film structure is complex, it is easy to deposit onto the substrate, and therefore it can be applied to next-generation semiconductor devices.

[0110] As an example, the prepared thin film can be a TiN or TiO2 thin film.

[0111] The following preferred embodiments and accompanying drawings are provided to illustrate the present invention. The embodiments and accompanying drawings are for illustrative purposes only. Those skilled in the art will understand that various changes and modifications can be made within the scope and technical concept of the present invention, and such changes and modifications should also fall under the appended claims.

[0112] [Example]

[0113] Examples 1-3

[0114] The growth inhibitors for thin film formation described in Table 1 below were prepared, and TiCl4 was prepared as a thin film precursor compound. The prepared growth inhibitors for thin film formation were placed in a metal container and supplied to a vaporizer heated to 150°C at a flow rate of 0.05 g / min using a Liquid Mass Flow Controller (LMFC) at room temperature. The growth inhibitors for thin film formation, vaporized in the vaporizer, were introduced into the deposition chamber containing the substrate for 1 second, followed by argon purging at 5000 sccm for 2 seconds. The pressure in the reaction chamber was controlled at 2.5 Torr. Next, the prepared TiCl4 was placed in another metal container and supplied to another vaporizer heated to 150°C at a flow rate of 0.05 g / min using a Liquid Mass Flow Controller (LMFC) at room temperature. TiCl4, vaporized in the vaporizer, is introduced into the deposition chamber for 1 second, followed by argon purging at 5000 sccm for 2 seconds. The pressure within the reaction chamber is maintained at 2.5 Torr. Next, ammonia is introduced as the reactive gas into the reaction chamber at 1000 sccm for 3 seconds, followed by argon purging for 3 seconds. The substrate to be formed is then heated to 460°C. This process is repeated 200 times to form a self-limiting atomic-layer TiN thin film.

[0115] Table 1:

[0116] category Growth inhibitors for thin film formation Example 1 tert-butyl bromide Example 2 1-Methyl-1-bromocyclohexane Examples 3-5 Tert-butyl iodide

[0117] Example 4

[0118] The growth inhibitors for thin film formation listed in Table 1 above were prepared, and TiCl4 was prepared as a thin film precursor compound. The prepared growth inhibitors for thin film formation were placed in a metal container and supplied at room temperature to a vaporizer heated to 150°C using a Liquid Mass Flow Controller (LMFC) at a flow rate of 0.05 g / min. The prepared TiCl4 was placed in another metal container and supplied at room temperature to another vaporizer heated to 150°C using a Liquid Mass Flow Controller (LMFC) at a flow rate of 0.05 g / min.

[0119] TiCl4, vaporized in the vaporizer, is introduced into the deposition chamber for 1 second, followed by argon purging at 5000 sccm for 2 seconds. The pressure inside the reaction chamber is maintained at 2.5 Torr. Next, a growth inhibitor for thin film formation, vaporized in the vaporizer, is introduced into the deposition chamber containing the substrate for 1 second, followed by argon purging at 5000 sccm for 2 seconds. The pressure inside the reaction chamber is maintained at 2.5 Torr. Next, ammonia is introduced into the reaction chamber as a reactive gas at 1000 sccm for 3 seconds, followed by argon purging for 3 seconds. The substrate to be formed into a metal thin film is then heated to 440–500°C. This process is repeated 200 times to form a self-limiting atomic-layer TiN thin film.

[0120] Example 5

[0121] The growth inhibitors for thin film formation described in Table 1 above were prepared, and Si2Cl6 was prepared as a thin film precursor compound. The prepared growth inhibitors for thin film formation were placed in a metal container and supplied at room temperature to a vaporizer heated to 150°C using a Liquid Mass Flow Controller (LMFC) at a flow rate of 0.05 g / min. The prepared Si2Cl6 was placed in another metal container and supplied at room temperature to another vaporizer heated to 150°C using a Liquid Mass Flow Controller (LMFC) at a flow rate of 0.05 g / min.

[0122] A growth inhibitor for thin film formation, vaporized in a vaporizer, is introduced into the deposition chamber containing the substrate for 1 second, followed by argon purging at 5000 sccm for 2 seconds. During this time, the pressure inside the reaction chamber is controlled at 2.5 Torr. Next, Si₂Cl₆, vaporized in a vaporizer, is introduced into the deposition chamber for 1 second, followed by argon purging at 5000 sccm for 2 seconds. During this time, the pressure inside the reaction chamber is controlled at 2.5 Torr. Next, ammonia is introduced into the reaction chamber as a reactive gas at 1000 sccm for 3 seconds, followed by plasma treatment at 200 W. Next, argon purging is performed for 3 seconds. During this time, the substrate to which the metal thin film is to be formed is heated to 460°C. This process is repeated 300 times to form a self-limiting atomic-layer SiN thin film.

[0123] Example 6

[0124] Except for the use of tert-butyl chloride as a growth inhibitor for film formation, the use of NbF5 as a film precursor compound, and the use of VFC instead of LDS for vaporization, a self-limiting atomic layer NbN film was formed by the same method as in Example 1.

[0125] Comparative Example 1

[0126] Except that no growth inhibitor for thin film formation was used and therefore the step of purging unadsorbed growth inhibitor for thin film formation was omitted, a TiN thin film was formed on the substrate by the same method as in Example 1.

[0127] Compare Examples 2 and 3

[0128] Except that pentane or cyclopentane was used instead of the growth inhibitors for thin film formation described in Table 1 above, TiN thin films were formed on the substrate using the same method as in Example 1.

[0129] Comparative Example 4

[0130] Except that no growth inhibitor for thin film formation was used and the step of purging unadsorbed growth inhibitor for thin film formation was omitted, a SiN thin film was formed on the substrate by the same method as in Example 5.

[0131] Comparative Example 5

[0132] Except for the absence of growth inhibitors for film formation, a self-limiting atomic layer NbN film was formed using the same method as in Example 6.

[0133] [Experimental Example]

[0134] 1) Sedimentary evaluation

[0135] As shown in Table 2 below, Example 1, which used tert-butyl bromide as a growth inhibitor for film formation, was compared with Comparative Example 1, which did not contain it. As a result, the deposition rate of Example 1 was... Compared to Comparative Example 1, the deposition rate decreased by more than 40%. It was confirmed that the remaining Examples 2 and 3, as well as Example 5, also had deposition rates similar to those of Example 1. Furthermore, it was confirmed that Comparative Examples 2 and 3, which used pentane or cyclopentane instead of the growth inhibitor for film formation of the present invention, also had deposition rates similar to those of Comparative Example 1. In this case, the decrease in deposition rate indicates a change from CVD deposition characteristics to ALD deposition characteristics, and therefore can be used as an indicator of improved step coverage characteristics.

[0136] Furthermore, to confirm whether the same effect could be achieved on SiN thin films, Example 5 was compared with Comparative Example 4, referring to Table 2 below. The results show that the deposition rate of Example 5 was... Compared with Comparative Example 4 Compared to that, it has decreased by more than 10%.

[0137] Figure 7 The images show the SIMS analysis of the SiN films prepared in Example 5 and Comparative Example 4. It can be confirmed that the Cl content in Example 5, shown in the right image, is significantly reduced compared to Comparative Example 4 shown in the left image.

[0138] Additionally, referring to Table 2 below, it can be confirmed that the deposition rate of Example 4 is... Comparative Example 1 with the one that did not use a growth inhibitor for film formation Compared to the previous year, this represents an increase of nearly 10%, and when the deposition temperature is increased to 500°C, it increases to [a certain percentage]. The increase was close to 16%. In Example 4, ter-butyl iodide was used as a growth inhibitor for film formation. The source precursor was first adsorbed, that is, after the film precursor was adsorbed, argon gas was purged, and then the growth inhibitor for film formation was supplied.

[0139] It can be confirmed that the deposition rate of Example 4 is actually increased compared with Comparative Example 1. However, unlike the prior art, the impurities do not increase with the increase of deposition rate. Instead, the impurities are unexpectedly reduced. Therefore, it provides another great advantage in terms of throughput.

[0140] Table 2:

[0141]

[0142] 2) Impurity reduction characteristics

[0143] To compare the impurity reduction characteristics, i.e., the process by-product reduction characteristics, of the deposited TiN films based on Examples 1-5 and Comparative Examples 1-2, SIMS analysis was performed, and the results are shown in Table 3 below. Figure 3 , Figure 4 In the middle, the reduction rate of Cl (%) was calculated according to mathematical formula 2.

[0144] [Mathematical Expression 2]

[0145]

[0146] Table 3:

[0147]

[0148] *Reference thickness of the sample film: 10 nm

[0149] As shown in Table 3 above, the Cl intensity of Examples 1 to 5, which used the growth inhibitor for thin film formation of the present invention, was significantly reduced compared with Comparative Examples 1 to 2, which did not use it, thus confirming its excellent impurity reduction characteristics.

[0150] Furthermore, comparing Example 3 with Example 4, it can be confirmed that the process method of Example 4 is very beneficial to the impurity reduction characteristics.

[0151] in addition, Figure 3 , Figure 4 The graph shows the process by-product reduction characteristics based on deposition temperature for Example 1 and Comparative Example 1, i.e., the Cl reduction rate. It can be confirmed that when the growth inhibitor for thin film formation of the present invention is used, the Cl intensity is significantly reduced at all deposition temperatures, especially in the range of 480 to 520°C.

[0152] In addition, such as Figure 9 As shown, compared to Comparative Example 5 (Ref NbF5) which did not use a growth inhibitor for film formation, Example 6, which used the growth inhibitor for film formation of the present invention (tert-butyl chloride) and replaced the film precursor with an Nb film precursor, showed a significant reduction in the intensity (c / s) of intrafilm contaminants F and C, thus confirming its excellent impurity reduction characteristics. More specifically, compared to Comparative Example 5 (F(c / s) = 116,925.65, C(c / s) = 1,466) used as a reference, Example 6 (F(c / s) = 75,197, C(c / s) = 656) using NbF5 as the film precursor showed a reduction of 35% and 55% in the intensity of intrafilm contaminants F and C, respectively, thus further confirming the excellent impurity reduction characteristics of the Nb film of the present invention.

[0153] 3) Reduction rate of film growth

[0154] Regarding the film growth rate of the TiN films deposited in Examples 1-5 and Comparative Examples 1-2, after measuring the thickness by ellipsometry, the film growth rate reduction rate was calculated using the result and Equation 1, and the result is shown in Table 4 below.

[0155] [Mathematical Expression 1]

[0156] Reduction in film growth rate per cycle (%) = [(Film growth rate per cycle with growth inhibitor used - Film growth rate per cycle without growth inhibitor used) / Film growth rate per cycle without growth inhibitor used] × 100

[0157] Table 4:

[0158]

[0159] As shown in Table 4 above, it can be confirmed that compared with Comparative Example 1, which did not use the growth inhibitor for thin film formation of the present invention, Examples 1 to 3, which used the growth inhibitor for thin film formation of the present invention, had a reduction rate of 10% to 40% per cycle, which is superior. Furthermore, it can be confirmed that compared with Comparative Example 2, Example 5 had a reduction rate of 17% per cycle in thin film growth, which is also superior.

[0160] Furthermore, when the process method was changed, Example 4 was compared with Comparative Example 1. Compared with Comparative Example 1, the deposition rate of Example 4 was actually increased. However, unlike the prior art, even with the increase in deposition rate, the impurity reduction characteristics were excellent, which provided another great advantage in terms of throughput.

[0161] 4) Step Coverage Characteristics

[0162] The step coverage of the TiN films deposited in Example 1 and Comparative Example 1 was confirmed using TEM, and the results are shown in Table 5 below. Figure 5 middle.

[0163] Table 5:

[0164] category Example 1 Comparative Example 1 Step coverage (%) 84 48

[0165] As shown in Table 5 above, it can be confirmed that the step coverage of Example 1, which used the growth inhibitor for thin film formation of the present invention, was significantly higher than that of Comparative Example 1, which did not use the growth inhibitor for thin film formation of the present invention. Additionally, refer to... Figure 5 The TEM images show that, compared to the TiN film deposited in Comparative Example 1 (TiCl4), the TiN film deposited in Example 1 (SP-TiCl4) exhibits superior uniformity of thickness and conformity at both the top and bottom. Furthermore, the cross-sections of the top and bottom layers can be visualized through... Figure 6 To explain, the top section is formed at a position 200 nm downward from the top, and the bottom section is formed at a position 100 nm upward from the bottom.

[0166] Reference example 1

[0167] Except that tert-butyl chloride was used as a growth inhibitor for film formation instead of tert-butyl bromide, a self-limiting atomic layer TiN film was formed by performing the process in the same manner as in Example 1. In order to compare the impurity reduction characteristics, i.e. the process by-product reduction characteristics, of the deposited TiN film with those of Example 1, SIMS analysis was performed, and the results are shown in Table 6 below.

[0168] Table 6:

[0169]

[0170] *Base thickness: 10nm

[0171] As shown in Table 6 above, compared with Reference Example 1 which used a growth inhibitor for chloride film formation, Example 1 which used the growth inhibitor for bromide film formation of the present invention had a greater Cl reduction rate, thus confirming that the impurity reduction characteristics were superior.

[0172] 5) Thin film crystallinity

[0173] Figure 8 The XRD patterns of Comparative Example 1 (Ref TiN) without added growth inhibitor for thin film formation, Example 4 (tert-Butyl Iodine (tert-BuI) with added growth inhibitor for thin film formation at a rate of 0.1 g / min, and Example 4 (tert-Butyl Iodine (tert-BuI) with added growth inhibitor for thin film formation at a rate of 0.01 g / min) confirm that when the film precursor compound is adsorbed first, followed by argon purging, and then the tert-Butyl Iodine (tert-BuI) growth inhibitor for thin film formation is adsorbed, as in Example 4, the film grains are larger, i.e., the crystallinity increases. The grain size can be determined by the (200) position of the TiN film (a higher and sharper peak at the 200 position indicates higher crystallinity), and when crystallinity increases in this way, it has the advantage of significantly improving resistivity.

[0174] 6) Thin film density

[0175] X-ray reflectance (XRR) analysis of Comparative Example 1 (Ref TiN) without added growth inhibitor, Example 4 (tert-butyl iodine (tert-BuI) with added growth inhibitor at a rate of 0.1 g / min, and Example 4 (tert-butyl iodine (tert-BuI)) with added growth inhibitor at a rate of 0.01 g / min, showed that the density of the TiN film prepared in Comparative Example 1 was 4.85 g / cm³. 3 However, in Example 4, the TiN film prepared using 0.01 g / min of tert-butyl iodine (tert-BuI) had a density of 5.00 g / cm³. 3 In Example 4, the TiN film prepared using 0.1 g / min of tert-butyl iodine (tert-BuI) had a density of 5.23 g / cm³. 3 Therefore, it can be confirmed that in Example 4, where the film precursor compound was first adsorbed, followed by argon purging and then adsorption of a growth inhibitor for film formation (tert-BuI), the film density increased significantly. Thus, the film of the present invention has the advantages of improving the bending characteristics of integrated structures with high aspect ratios, such as DRAM capacitors, and having superior barrier metal properties.

[0176] Therefore, the present invention can provide a film density of 4.95 g / cm³. 3 The above, preferably 5.00 g / cm³ 3 Specifically, the values ​​are 4.95–5.50 g / cm³. 3 Preferably, it is 5.0–5.3 g / cm³. 3 of film.

Claims

1. A method for forming a thin film, characterized in that, Includes the following steps: A thin film is formed by injecting a growth inhibitor for thin film formation, represented by Chemical Formula 1, into an ALD chamber and allowing it to adsorb onto the surface of the mounted substrate. The thin film serves as an anti-diffusion film located between the silicon layer of the doped semiconductor and the interlayer metal wiring material. [Chemical Formula 1] A n B m X o Y i Z j Wherein, A is carbon; B is hydrogen or an alkyl group having 1 to 3 carbon atoms; X is one of bromine (Br) and iodine (I); Y and Z are each independently selected from one or more of oxygen, nitrogen, sulfur, and fluorine, and are different from each other; n is an integer from 1 to 15; o is 1; m is 0 to 2n+1; i and j are integers from 1 to 3. The growth inhibitor for film formation is liquid at room temperature (22°C) with a density of 0.8–1.5 g / cm³. 3 Its vapor pressure at 20℃ is 1–300 mmHg, and its solubility in water at 25℃ is less than 160 mg / L. The thin film satisfies at least one of the following: resistivity of 10 to 100 μΩ·cm and step coverage of 80% or more.

2. The thin film forming method according to claim 1, characterized in that, Includes the following steps: Step i) The thin film is vaporized using a growth inhibitor and adsorbed onto the surface of the substrate loaded into the ALD chamber. Step ii) involves first purging the interior of the ALD chamber using purge gas; Step iii) vaporizes the thin film precursor compound and adsorbs it onto the surface of the substrate loaded into the ALD chamber; Step iv) involves a second purging of the ALD chamber using purge gas; Step v), supplying the reactant gas into the ALD chamber; and Step vi), the interior of the ALD chamber is purged a third time using purge gas.

3. The thin film forming method according to claim 1, characterized in that, Includes the following steps: Step i) vaporizes the thin film precursor compound and adsorbs it onto the surface of the substrate loaded into the ALD chamber; Step ii) involves first purging the interior of the ALD chamber using purge gas; Step iii) The thin film is vaporized using a growth inhibitor and adsorbed onto the surface of the substrate loaded into the ALD chamber. Step iv) involves a second purging of the ALD chamber using purge gas; Step v), supplying the reactant gas into the ALD chamber; and Step vi), the interior of the ALD chamber is purged a third time using purge gas.

4. The thin film forming method according to claim 2 or 3, characterized in that, The growth inhibitor for film formation and the film precursor compound are transferred into the ALD chamber via VFC, DLI, or LDS.

5. The thin film forming method according to claim 2 or 3, characterized in that, The ratio of the growth inhibitor for film formation to the amount of the film precursor compound added in the ALD chamber (mg / cycle) is 1:1.5 to 1:

20.

6. The thin film forming method according to claim 2 or 3, characterized in that, The reduction rate of film growth rate (Å / cycle) per cycle calculated according to Formula 1 for the aforementioned film formation method is less than -5%. [Mathematical Expression 1] The reduction rate of film growth rate per cycle (%) = [(film growth rate per cycle when using growth inhibitor for film formation - film growth rate per cycle when not using growth inhibitor for film formation) / film growth rate per cycle when not using growth inhibitor for film formation] × 100.

7. The thin film forming method according to claim 2 or 3, characterized in that, According to SIMS measurements, the residual halogen intensity (c / s) in the film formed by the aforementioned film formation method after 200 cycles is below 10,000.

8. The thin film forming method according to claim 2 or 3, characterized in that, The reactant gas is a reducing agent, a nitriding agent, or an oxidizing agent.

9. A semiconductor substrate, characterized in that, It is manufactured by the thin film forming method according to claim 1.

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