Growth inhibitor for forming thin film, thin film forming method using the same, and semiconductor substrate manufactured therefrom

Abstract

SOLUTION: To provide a method for forming a thin film using a growth inhibitor for forming thin film which is a compound represented by Chemical Formula 1 below: [Chemical Formula 1] AnBmXoYiZj (A is carbon or silicon; B is hydrogen or alkyl having 1 to 3 carbon atoms; X is a leaving group having a bond dissociation energy of 50 to 350 KJ / mol; Y and Z are independently one or more selected from a group consisting of 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 greater; m is from 0 to 2n+1; and i and j are each an integer of 0 to 3).EFFECT: The present invention brings about an effect of providing: a growth inhibitor for forming a thin film, that can inhibit side reactions to reduce a thin film growth rate and remove process by-products from within a thin film to greatly improve step coverage and thin film thickness uniformity even when the thin film is formed on a substrate having a complicated structure; a thin film forming method using same; and a semiconductor substrate manufactured therefrom.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a growth inhibitor for thin film formation, a method for forming a thin film using the same, and a thin film produced from the same. More specifically, the present invention relates to a semiconductor substrate that can suppress side reactions and appropriately grow a thin film. By reducing the thickness and removing process by-products in the thin film, corrosion and degradation can be prevented, and complex structures can be Even when forming a thin film on a substrate having a A growth inhibitor for thin film formation that significantly improves the uniformity of the film thickness and the thickness of the thin film, The present invention relates to methods of forming and semiconductor substrates produced therefrom. [Background technology]

[0002] The integration density of memory and non-memory semiconductor devices is increasing day by day, and their structures are becoming increasingly complex. As a result, the step coverage (step coverage) of various thin films deposited on a substrate has become more difficult. erage) is gradually becoming more and more important.

[0003] The semiconductor thin film is made of metal nitride, metal oxide, metal silicide, or the like. Examples include titanium nitride (TiN), tantalum nitride (TaN), and zirconium nitride (ZrN ), and the thin film generally comprises a doped semiconductor silicon layer and an interlayer The diffusion prevention film (d However, tungsten (W) thin film is used as an infusion barrier. It is used as an adhesion layer when vapor-depositing onto a substrate.

[0004] In order to obtain excellent and uniform properties of the thin film deposited on the substrate, Therefore, the thin film must have high step coverage. By utilizing surface reactions rather than chemical vapor deposition (CVD) processes, The ALD (atomic layer deposition) process is being used to However, there are still problems to be solved in order to achieve 100% step coverage. exist.

[0005] In addition, titanium nitride (TiN), which is a representative metal nitride, is deposited on the substrate. In the case of titanium tetrachloride (TiCl4) used for this purpose, the produced thin film contains chlorides. The by-products of the process remain and induce corrosion of metals such as aluminum. However, the problem of non-volatile by-products being generated leads to deterioration of the film quality.

[0006] Therefore, it is possible to form thin films with complex structures, and the thin films do not corrode the interlayer wiring materials. It is necessary to develop a method for forming the semiconductor substrate and the semiconductor substrate manufactured from the method. It is. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Korean Patent Publication No. 2006-0037241 Summary of the Invention [Problem to be solved by the invention]

[0008] In order to solve the above problems of the prior art, the present invention provides a method for forming a thin film by suppressing side reactions. Prevents corrosion and degradation by appropriately reducing the elongation rate and removing process by-products in the thin film In addition, even when forming a thin film on a substrate with a complex structure, the step coverage is excellent. verage) and a growth inhibitor for thin film formation that significantly improves the uniformity of the thin film thickness, The present invention aims to provide a thin film forming method using the above-mentioned method, and a semiconductor substrate manufactured using the method. .

[0009] The present invention improves the density and electrical properties of a thin film by improving the crystallinity of the thin film. The purpose is to

[0010] The above and other objects of the present invention can be achieved by the present invention described below. This can be done. [Means for solving the problem]

[0011] In order to achieve the above object, the present invention provides a compound represented by the following formula 1: [Chemical formula 1] AnBmXoYiZj

[0012] (The above A is carbon or silicon, and the above B is hydrogen or an alkyl group having 1 to 3 carbon atoms.) and X is the bond dissociation energy. is a leaving group having a molecular weight of 50 to 350 KJ / mol, Y and Z are independently selected from the group consisting of oxygen, nitrogen, sulfur, and fluorine. wherein n is an integer of 1 to 15, and o is 1. or more, m is an integer of 0 to 2n+1, and the i and j are integers of 0 to 3. The present invention provides a growth inhibitor for thin film formation, which is a compound that is

[0013] The growth inhibitor for thin film formation of the present invention can also be provided as a film quality improving agent.

[0014] In addition, the present invention provides a method for forming a thin film by injecting the growth inhibitor into an ALD chamber. and adsorbing the thin film on the surface of the loaded substrate. .

[0015] The present invention also provides a semiconductor substrate manufactured by the above-mentioned thin film formation method. Effect of the Invention

[0016] According to the present invention, side reactions are suppressed, the deposition rate is reduced, and the thin film growth rate is appropriately reduced. Furthermore, by removing process by-products from within the thin film, corrosion and degradation are prevented, and complex structures can be effectively When forming a thin film on a substrate, the step coverage and the thinness are also required. Growth inhibitor for thin film formation that significantly improves uniformity of film thickness and thin film formation method using the same and a semiconductor substrate manufactured therefrom.

[0017] In addition, according to the present invention, the crystallinity of the thin film is improved, thereby improving the density and electrical properties of the thin film. The purpose is to improve the characteristics. [Brief description of the drawings]

[0018] [Figure 1] FIG. 1 is a process diagram for explaining a conventional ALD process. [Diagram 2] FIG. 1 is a process diagram illustrating an ALD process according to one embodiment of the present invention. [Diagram 3] 1 is a SIMS analysis graph (1) showing the reduction rate of Cl element and the like depending on the deposition temperature for Example 1 (SP-TiCl4) of the present invention and Comparative Example 1 (TiCl4). [Figure 4] 1 is a SIMS analysis graph (2) showing the reduction rate of Cl element and the like depending on the deposition temperature for Example 1 (SP-TiCl4) of the present invention and Comparative Example 1 (TiCl4). [Diagram 5]3 is a TEM photograph of a cross section near the top and bottom of a TIN thin film formed in Example 1 (SP-TiCl4) of the present invention and Comparative Example 1 (TiCl4). [Figure 6] 6 is an explanatory diagram of the cross-sectional positions of the top and bottom of FIG. 5. FIG. [Figure 7] 1 is a SIMS analysis graph of SiN thin films produced in Example 5 and Comparative Example 4. [Figure 8] This is an XRD analysis graph for a case where no growth inhibitor for thin film formation was added (Ref TiN), as in Comparative Example 1, a case where a growth inhibitor for thin film formation was added in an amount of 0.1 g / min in Example 4 (tert-BuI (0.1 g / min)), and a case where a growth inhibitor for thin film formation was added in an amount of 0.1 g / min in Example 4 (tert-BuI (0.1 g / min)). [Figure 9] 1 is a graph showing the analysis of carbon concentrations in thin films in Example 6 and Comparative Examples 2 and 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The following describes the growth inhibitor for thin film formation described herein, a method for forming a thin film using the same, and a method for producing the same. The semiconductor substrate thus formed will now be described in detail.

[0020] The inventors have applied a thin film to the surface of a substrate loaded inside an ALD chamber. Before adsorption of the precursor compound, a compound containing a substituent with a predetermined bond dissociation energy is diluted with When it is first adsorbed as a film growth inhibitor, the growth rate of the thin film formed after deposition is significantly reduced. This significantly improves step coverage, and the halides that remained as process by-products are eliminated. It was also confirmed that the amount of loaded material inside the ALD chamber was significantly reduced. A thin film precursor compound is first adsorbed on the surface of the substrate, and a halogen-substituted thin film having a predetermined structure is formed. When the compound was adsorbed as a thin film growth inhibitor, it behaved as a film quality improver, contrary to expectations. The growth rate of the thin film formed by this process is increased, and the halides remaining as process by-products are It was confirmed that the density and resistivity of the thin film were significantly improved. Based on this, the inventors further pursued research and completed the present invention.

[0021] The growth inhibitor for thin film formation of the present invention is represented by the following chemical formula 1 [Chemical formula 1] AnBmXoYiZj

[0022] (The above A is carbon or silicon, and the above B is hydrogen or an alkyl group having 1 to 3 carbon atoms.) and X is the bond dissociation energy. is a leaving group having a molecular weight of 50 to 350 KJ / mol, Y and Z are independently one selected from the group consisting of oxygen, nitrogen, sulfur, and fluorine. or more, which are not the same as each other, and n is an integer of 1 to 15, and o is an integer of 1 or more. m is a number ranging from 0 to 2n+1, and the i and j are integers ranging from 0 to 3. In such a case, the compound is characterized by suppressing side reactions during thin film formation. This reduces the thin film growth rate and also removes process by-products within the thin film, preventing corrosion and degradation. The step coverage is reduced, and even when a thin film is formed on a substrate with a complex structure, p coverage) and the uniformity of the thin film thickness are significantly improved. .

[0023] The B is preferably hydrogen or methyl, and the n is preferably an integer of 2 to 15. More preferably, it is an integer from 2 to 10, even more preferably, it is an integer from 2 to 6, and even more preferably, it is an integer from 4 to 8. Within this range, the effect of removing process by-products is large and the step coverage is excellent. do.

[0024] In the above formula 1, X is preferably a bond dissociation energy. A leaving group having a cation energy of 50 to 350 KJ / mol is more preferred. Leaving groups with bond dissociation energies of 50 to 325 KJ / mol More preferably, it is bond dissociation energy. Leaving group with ion energy of 50-300KJ / mol group), in which case side reactions are suppressed and process by-products are more effectively removed. This has the effect of

[0025] The bond dissociation energies in this description were calculated using a quantum chemistry program (Gaussian09). All calculations are based on temperature: 460°C, pressure: 1 torr. and scale: 0.9804, Method (DFT / B3LYP) and Basis Sets (6-31G(d,p), excluding iodine: LanL2DZ) Based on this, it is calculated using the following formula 3.

[0026] [Formula 3] BDE = EA + EB -EAB

[0027] (EAB is the thermal energy of the optimized compound, EA and EB are the radicals, respectively.) The thermal energy of radicals A and B is the thermal energy of radicals A and B. To be specified.

[0028] In the formula 1, preferred examples of X include mesyl and tosyl. yl), halogen group, diazonium (azonium) (-N2 + ), Perfluoroal arylsulfonate (-OSO2R'), alcohol cation (-O + HR''), Knight nitrate (-ONO2), ammonium (-N H3), monoalkylammonium group, dialkyl Dialkylammonium group, trialkylammonium group (trialkylammonium), dialkyl ether cation (-O + R1R2 ), phosphate group (-OPO(OH)2) or thioether cation (-S + R3R4) In this case, it is possible to suppress side reactions and more effectively remove process by-products.

[0029] In the above Chemical Formula 1, the o is preferably an integer of 1 to 5, and more preferably Preferably, it is an integer of 1 to 3, and more preferably, it is 1 or 2. Within this range, the deposition rate is significantly reduced, and the step coverage is more effectively improved. This has the advantage that

[0030] The m is preferably 1 to 2n+1, and more preferably 3 to 2n+1. Within this range, the effect of removing process by-products is large, and step coverage is excellent.

[0031] As preferred examples, Y and Z are independently selected from the group consisting of oxygen, nitrogen and fluorine. One or more selected types are not equal to each other.

[0032] In a preferred embodiment, i and j are not both 0, and in a specific embodiment, they are integers from 1 to 3. Possible.

[0033] The compound represented by the formula 1 is preferably a branched, cyclic or aromatic compound. Specific examples include tert-butyl bromide and 1-methyl-1-bromocyclohexane. xanthane, 1-iodopropane, 1-iodobutane Obutane, 1-iodo-2-methylpropane pane), 1-iodo-1-isopropylcyclohexane pylcyclohexane), 1-iodo-4-nitrobenzene trobenzene, 1-iodo-4-methoxybenzene xybenzene, 1-iodo-2-methylpentane entane), 1-iodo-4-trifluoromethylbenzene (1-iodo-4-trifluoromethylbenzene uroromethylbenzene), tert-butyl iodide iodide) and 1-methyl-1-iodocyclohexane ocyclohexane), 1-bromo-4-chlorobenzene (1-bromo-4-chlorobenzene orobenzene), 1-bromopropane, 1-bromo Butane (1-bromobutane), 1-bromopentane e), 1-bromohexane, 1-bromo-2-methylpropane (1 -bromo-2-methylpropane, 1-bromooctane ctance), 1-bromonaphthalene, 1-bromonaphthalene 1-bromo-4-iodobenzene and 1-bromo-4-diiodobenzene 1-bromo-4-nitrobenzene In this case, the effect of removing process by-products is large, and the step coverage is improved and the film is It is highly effective in improving quality.

[0034] The compound represented by the formula 1 is preferably prepared by atomic layer deposition (ALD; In this case, it acts as a growth inhibitor without interfering with the adsorption of the thin film precursor compound. This effectively protects the surface of the substrate and effectively removes process by-products. There is an advantage to removing it.

[0035] The compound represented by the formula 1 is preferably liquid at room temperature (22° C.) and has a high density. Gravity: 0.8~2.5g / cm 3 or 0.8~1.5g / cm 3 and the vapor pressure (20℃) is 0.1 to 300 mmHg or 1 to 300 mmHg, and the solubility in water (25°C) Within this range, the step coverage and the uniformity of the thin film thickness can be achieved. It has an excellent effect in improving the adhesion and film quality.

[0036] More preferably, the compound represented by Chemical Formula 1 has a density of 0.85 to 2.0 g / cm 3 or 0.85~1.3g / cm 3 The vapor pressure (20℃) is 1 to 260 mmHg. The solubility in water (25°C) may be 160 mg / L or less, and within this range This has an excellent effect on improving step coverage, thin film thickness uniformity, and film quality.

[0037] In the method for forming a thin film of the present invention, a compound represented by the following chemical formula 1 is [Chemical formula 1] AnBmXoYiZj

[0038] (The above A is carbon or silicon, and the above B is hydrogen or an alkyl group having 1 to 3 carbon atoms.) and X is the bond dissociation energy. is a leaving group having a molecular weight of 50 to 350 KJ / mol, Y and Z are independently selected from the group consisting of oxygen, nitrogen, sulfur, and fluorine. wherein n is an integer of 1 to 15, and o is 1. or more, m is an integer of 0 to 2n+1, and the i and j are integers of 0 to 3. The growth inhibitor for thin film formation is injected into the ALD chamber and loaded. g) a step of adsorbing the compound on the substrate surface, Suppresses deposition rate, reduces thin film growth rate, and removes process by-products in the thin film. This allows for good step coverage even when forming a thin film on a substrate with a complex structure. p coverage) and the thickness uniformity of the thin film are significantly improved.

[0039] The step of adsorbing the growth inhibitor for forming a thin film on the surface of the substrate includes forming a thin film on the surface of the substrate. The feeding time of the growth inhibitor for growth is preferably Preferably, the reaction time is 1 to 10 seconds, more preferably 1 to 5 seconds, even more preferably 2 to 5 seconds, and even more preferably Within this range, the thin film growth rate is low, and the step coverage and economy are excellent. This has the advantage that:

[0040] The feeding time of the growth inhibitor for thin film formation in this description is The standard is a chamber volume of 15 to 20 L and a flow rate of 0.5 to 5 mg / s. More specifically, The standard is a cylinder volume of 18 L and a flow rate of 1 to 2 mg / s.

[0041] In a preferred embodiment, the method for forming the thin film comprises: i) vaporizing a growth inhibitor for forming the thin film; ii) adsorbing the compound on a surface of a substrate loaded in an ALD chamber; iii) purging the inside of the chamber with a purge gas; and iii) vaporizing the thin film precursor compound. adsorbing the compound on a surface of a substrate loaded in the ALD chamber; iv) adsorbing the compound on the surface of the substrate loaded in the ALD chamber; a step of purging the inside of the chamber with a purge gas; and a step of purging the inside of the ALD chamber with a reaction gas. and vi) third purging the interior of the ALD chamber with a purge gas. In such a case, the thin film growth rate is appropriately reduced, and Even when the deposition temperature is high, the process by-products generated are effectively removed, and the resistivity of the thin film is low. The advantages are that the surface area is reduced and step coverage is greatly improved.

[0042] In another preferred embodiment, the method for forming a thin film includes the steps of: i) vaporizing a thin film precursor compound; and adsorbing the ALDP on a surface of a substrate loaded in an ALD chamber; D) purging the inside of the chamber with a purge gas; iii) a growth inhibitor for forming the thin film. and adsorbing onto the surface of a substrate loaded in an ALD chamber; iv). v) purging the interior of the ALD chamber with a purge gas; and vi) supplying a reaction gas to the inside of the ALD chamber with a purge gas for a third time. In such a case, the thin film growth rate is increased, and the thin film Even if the deposition temperature is high during formation, the process by-products generated can be effectively removed. This has the advantage that the resistivity of the thin film is reduced and the thin film density and crystallinity are greatly improved.

[0043] The growth inhibitor and the thin film precursor compound for forming the thin film are preferably used in the VFC method, DLI method, The ALD chamber may be transferred to the ALD chamber by either the LD or LDS method, and more preferably by the LD method. The material is transferred into the ALD chamber using the S method.

[0044] The amount of the growth inhibitor for forming the thin film and the precursor compound added to the ALD chamber ( The ratio of (mg / cycle) may be preferably 1:1.5 to 1:20, and more preferably The ratio is preferably 1:2 to 1:15, more preferably 1:2 to 1:12, and further preferably More preferably, the ratio is 1:2.5 to 1:10. Within this range, the thin film growth rate per cycle is The reduction rate of the GPC is high, and the reduction of process by-products is significant.

[0045] The precursor compound of the thin film is a thin film precursor typically used in ALD (atomic layer deposition). There is no particular limitation as long as it is a compound, but it is preferably a metal film precursor compound or a metal oxide film precursor. compound, a metal nitride film precursor compound or a silicon nitride film precursor compound, , preferably tungsten, cobalt, chromium, aluminum, hafnium, vanadium , niobium, germanium, lanthanum group elements, actinium group elements, gallium, tantalum, Made of zirconium, ruthenium, copper, titanium, nickel, iridium, and molybdenum. The compound may include one or more selected from the group consisting of the following:

[0046] The metal film precursor, the metal oxide film precursor, and the metal nitride film precursor are, for example, Metal halides, metal alkoxides, alkyl metal compounds, metal amino compounds, metal carbo cyclopentadienyl compounds, and substituted or unsubstituted cyclopentadienyl metal compounds, etc. The number of the above-mentioned compounds may be one or more, but is not limited thereto.

[0047] As a specific example, the metal film precursor, the metal oxide film precursor, and the metal nitride film precursor are They are tetrachlorotitanium and tetrachlorojama, respectively. tetrachlorogemanium, tetrachlorotin lorotin), tris(isopropyl)ethylmethylaminogermanium (tris (isopropyl)ethylmethyl aminogermanium), Tetraethoxylgermanium, tetramethyl Tetramethyl tin, tetraethyl tin l tin, bisacetylacetonate tin), trimethylaluminum, tetra Tetrakis(dimethylamino)germanium )germanium), bis(n-butylamino)germanium ylamino)germanium), tetrakis(ethylmethylamino)tin (te trakis(ethylmethylamino)tin), tetrakis(dimethylamino)tin tetrakis(dimethylamino)tin, Co2(CO )8(dicobalt octacarbonyl), Cp2Co(biscyclo pentadienylcobalt), Co(CO)3(NO)(cobalt tr icarbonyl nitrosyl), and CpCo(CO)2(cabalt d icarbonyl cyclopentadienyl) and the like. There may be one or more of these, but the present invention is not limited thereto.

[0048] The silicon nitride film precursor may be, for example, SiH4, SiCl4, SiF4, or SiC l2H2, Si2Cl6, TEOS, DIPAS, BTBAS, (NH2)Si(NHM e)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 i Pr)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 P) 3. (NEt2)Si(NH n Bu), (NEt2)Si(NH i Bu), (NEt 2)Si(NH tBu)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(N H 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) Born i Pr)3、(N n Bu2)Si(NH n Bu)3、(N n Bu2)Si(N H i Bu)3、(N n Bu2)Si(NH t Bu)3、(N i Bu2)Si(NHMe) 3、(N i Bu2)Si(NHEt)3、(Ni 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) Born i Bu)3、(N i Bu2)Si(NH t Bu)3、(N t Bu2)Si(N HMe)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)2S i(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( NHMe2)2、(NMe2)2Si(NHEt)2、(NMe2)2Si(NH n Pr) 2、(NMe2)2Si(NH i Pr)2、(NMe2)2Si(NH n Bu)2、(N Me2)2Si(NH i Bu)2、(NMe2)2Si(NH t Bu)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)、(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)2S i(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(NHE t)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(NHi Pr)2、(N n Bu2)2Si(NH n Bu)2、(N n Bu2)2 Born i Bu)2、(N n Bu2)2Si(NH t Bu)2、(N i Bu2)2Si (NHMe)2、(N i Bu2)2Si(NHEt)2、(N i Bu2)2Si(NH n Pr)、(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 B u2)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)2 Born t Bu)2、Si(HNCH2CH2NH)2、Si(MeNCH2CH2N Me)2、Si(EtNCH2CH2NEt)2、Si( n PrNCH2CH2N n Pr )2、Si( i PrNCH2CH2N i Pr)2、Si( n BuNCH2CH2N nBu )2、Si( i BuNCH2CH2N i Bu)2、Si( t BuNCH2CH2N t Bu )2、Si(HNCHCHNH)2、Si(MeNCHCHNMe)2、Si(EtNC HCHNEt)2、Si( n PrNCHCHN n Pr)2、Si( i PrNCHCHN i Pr)2、Si( n BuNCHCHN n Bu)2、Si( i BuNCHCHN i Bu)2 ,Be( t BuNCHCHN t Group)2、(HNCHCHNH)Si(HNCH2CH2 NH)、(MeNCHCHNMe)Si(MeNCH2CHNMe)、(EtNCHCH NEt)Si(EtNCH2CH2NEt)、( n PrNCHCHN n Pr)If( n P rNCH2CH2N n Pr)、( i PrNCHCHN i Pr)If( i PrNCH2CH 2N i Pr)、( n BuNCHCHN n This)Si( n BuNCH2CH2N n Bu)、 ( i BuNCHCHN i This)Si( i BuNCH2CH2N i Bu)、( t BuNCH CHN t This)Si( t BuNCH2CH2N t Bu)、(NH t<h2 style=";text-align:left;direction:ltr">Bu)2Si(HNC<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> H2CH2NH)、(NH<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu)2Si(MeNCH2CH2NMe)、(NH<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> )2Si(EtNCH2CH2NEt)、(NH<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu)2Si(<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> PrNCH2CH2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Pr)、(NH<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu)2Si(<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> PrNCH2CH2N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr)、(NH<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2Si(<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> BuNCH2CH2N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Bu)、(NH<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu)2Si(<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> BuNCH2CH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Bu)、(NH<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu)2Si(<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> BuNCH2CH2N<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu)、(NH<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> )2Si(HNCHCHNH)、(NH<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu)2Si(MeNCHCHNMe)、(N<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu)2Si(EtNCHCHNEt)、(NH<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu)2Si(<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> PrNCHCH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Pr)、(NH<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu)2Si(<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> PrNCHCHN<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr)、(NH<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu)2S<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> i(<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> BuNCHCHN<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Bu)、(NH<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu)2Si(<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> BuNCHCHN<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Bu)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (NH<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu)2Si(<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> BuNCHCHN<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu)、(<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> PrNCH2CH2N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> P<h2 style=";text-align:left;direction:ltr"> r) Si(NHMe)2, ( i PrNCH2CH2N i Pr)Si(NHEt), ( i P rNCH2CH2N i Pr)Si(NH n Pr)2, ( i PrNCH2CH2N i P) 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 Pr NCHCHN 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 Bu)2, ( i PrNCHCHN i Pr)Si(NH i Bu)2 and Beauty( i PrNCHCHN i Pr)Si(NH t One or more selected from the group consisting of It can be, but is not limited to, the above.

[0049] The above n Pr stands for n-propyl.i Pr stands for iso-propyl n Bu is n -butyl, i Bu is isobutyl, t Bu means tert-butyl.

[0050] The thin film precursor compound may be titanium tetrahalide in one preferred embodiment. do.

[0051] The titanium tetrahalide can be used as a metal precursor for a thin film-forming composition. can.

[0052] The titanium tetrahalides include, for example, TiF4, TiCl4, TiBr4, and TiI4, for example, T From the economical viewpoint, iCl4 is preferable, but the present invention is not limited to this.

[0053] The titanium tetrahalide has excellent thermal stability and exists in a liquid state without being decomposed at room temperature. Therefore, it is useful as a precursor for ALD (atomic layer deposition) to deposit thin films. It can be used for.

[0054] For example, the thin film precursor compound is mixed with a non-polar solvent and then introduced into the chamber. In this case, there is an advantage that the viscosity and vapor pressure of the thin film precursor compound can be easily adjusted.

[0055] The non-polar solvent is preferably selected from the group consisting of alkanes and cycloalkanes. In this case, the reactivity and solubility are low, and moisture control is easy. Although it contains an organic solvent that is easy to dissolve, it has good step coverage even when the deposition temperature rises during thin film formation. The advantage is that it improves the overall p coverage.

[0056] In a more preferred example, the non-polar solvent is a C1 to C10 alkane. or a C3 to C10 cycloalkane; Preferably, it is a C3 to C10 cycloalkane. In this case, It has the advantages of low reactivity and solubility, making moisture control easy.

[0057] In this description, C1, C3 etc. refer to carbon numbers.

[0058] The cycloalkane may preferably be a C3 to C10 monocycloalkane. Among the monocycloalkanes, cyclopentane is Since it is liquid at room temperature and has the highest vapor pressure, it is preferred for the vapor phase deposition process. However, the present invention is not limited to the above.

[0059] The non-polar solvent preferably has a solubility in water (at 25° C.) of 200 mg / L or less, for example. The concentration is preferably 50 to 200 mg / L, and more preferably 135 to 175 mg / L. It has the advantage of being low in reactivity with thin film precursor compounds and easy moisture management. do.

[0060] The solubility in this description is based on the measurement method and standards commonly used in the technical field to which the present invention pertains. As long as the method is based on the above, there is no particular limitation. For example, a saturated solution is measured by HPLC. It is possible.

[0061] The non-polar solvent is preferably in an amount of about 100% by weight based on the total weight of the thin film precursor compound and the non-polar solvent. The content may be 5 to 95% by weight, more preferably 10 to 90% by weight, It is preferably contained in an amount of 40 to 90% by weight, and most preferably contained in an amount of 70 to 90% by weight. It is possible.

[0062] If the content of the non-polar solvent is more than the upper limit, impurities may be generated. The resistance and the number of impurities in the thin film increase, and the organic solvent content is below the lower limit. When the solvent is fully added, the effect of improving the step coverage by adding the solvent and the effect of removing chlorine (Cl) ions are However, it has the disadvantage that it is less effective in reducing impurities such as fluorine.

[0063] The thin film formation method may, for example, have a thin film growth rate per cycle, which is calculated by the following Equation 1: The decrease rate of (Å / Cycle) is −5% or less, preferably −10% or less, and more preferably is -20% or less, more preferably -30% or less, and even more preferably -40% or less. , and most preferably -45% or less. Within this range, the step coverage and the uniformity of the film thickness are Excellent in.

[0064] [Formula 1] Decrease rate of thin film growth rate per cycle (%) = [(When a growth inhibitor for thin film formation is used Thin film growth rate per cycle when no growth inhibitor for thin film formation was used Thin film growth rate per cycle) / per cycle without the use of a thin film growth inhibitor [thin film growth rate] x 100

[0065] In the above-mentioned thin film formation method, the thin film formed after 200 cycles was measured by SIMS. The residual halogen intensity (c / s) in the thin film is preferably 10,000 or less, more preferably Preferably, the number is 8,000 or less, more preferably 7,000 or less, and even more preferably 6,000 or less. 0 or less, and within this range, the effect of preventing corrosion and deterioration is excellent. can be.

[0066] In this description, purging is preferably performed at 1,000 to 10,000 sccm , more preferably 2,000 to 7,000 sccm, and even more preferably 2,500 to 6, 000 sccm, and within this range, the thin film growth rate per cycle is preferably low. This has the effect of reducing the amount of process by-products.

[0067] The ALD (atomic layer deposition) process is used for integrated circuits (ICs) that require high aspect ratios. This is extremely beneficial in the creation of self-limiting integrated circuits. Excellent conformality and uniformity due to efficient thin film growth mechanism Advantages include uniformity, and precise thickness control.

[0068] The thin film formation method may be carried out at a deposition temperature in the range of 50 to 900° C., for example. The deposition temperature is preferably in the range of 300 to 700°C, more preferably 350 to 600°C. The deposition temperature is preferably in the range of 400 to 550°C. It is more preferably carried out at a deposition temperature in the range of 400 to 500° C. Within this range, the ALD process characteristics are realized and a thin film with excellent film quality is grown. This has the effect of making people do so.

[0069] The thin film formation method is carried out, for example, at a deposition pressure in the range of 0.1 to 10 Torr. The deposition pressure is preferably in the range of 0.5 to 5 Torr, and most preferably in the range of 1 to 3 Torr. The deposition pressure is in the range of 0.25 orr, and within this range, a thin film of uniform thickness can be obtained. It's effective.

[0070] In this description, deposition temperature and deposition pressure refer to the temperature and pressure established in a deposition chamber. or as the temperature and pressure applied to the substrate in the deposition chamber. It is possible.

[0071] The thin film forming method preferably includes introducing a growth inhibitor for forming the thin film into a chamber. before the step of forming the thin film, the temperature in the chamber is increased to a deposition temperature; and / or Before the growth inhibitor is introduced into the chamber, an inert gas is injected into the chamber to purge it. It may include steps.

[0072] The present invention also provides a thin film manufacturing apparatus capable of implementing the thin film manufacturing method, comprising: D chamber, a first vaporizer for vaporizing the growth inhibitor for thin film formation, A first means for transporting the inhibitor into the ALD chamber, a second means for vaporizing the Ti-based thin film precursor, a vaporizer and a second transport means for transporting the vaporized Ti-based thin film precursor to an ALD chamber; The vaporizer and the transport means may include a thin film manufacturing apparatus according to the present invention. There are no particular limitations as long as the vaporizer and transport means are those commonly used in the technical field.

[0073] As a specific example, the thin film formation method will be described below. First, the substrate on which the thin film is to be formed is placed in a deposition chamber capable of atomic layer deposition. do.

[0074] The substrate may include a semiconductor substrate such as a silicon substrate, silicon oxide, or the like.

[0075] The substrate may further have a conductive or insulating layer formed thereon.

[0076] The deposition chamber is provided with a deposition chamber for depositing a thin film on a substrate, the deposition chamber being provided with a deposition chamber for depositing a thin film on the substrate. and a thin film precursor compound or a mixture of the same and a non-polar solvent, prepare.

[0077] Then, the prepared thin film formation inhibitor is injected into the vaporizer and then transformed into a vapor phase. The thin film formation inhibitor is transferred to the deposition chamber and adsorbed on the substrate, and the unadsorbed thin film formation inhibitor is purged (p urging).

[0078] Next, the prepared thin film precursor compound or a mixture of this and a non-polar solvent is injected into the vaporizer. After that, it is converted to the vapor phase and transferred to a deposition chamber where it is adsorbed onto the substrate, and then the unadsorbed thin film is removed. The film-forming composition is purged.

[0079] In this description, the inhibitors and precursor compounds for forming thin films are delivered to a deposition chamber. One example of the method is mass flow controller (MFC). A method of transporting evaporated gas using the Vapor Flow Control (Vapor Flow Control) method. A method of transferring liquids using the Liquid Phase Flow Control (VFC) or Liquid Phase Flow Control (LMFC) method. The formula (Liquid Delivery System; LDS) can be used, Preferably, the LDS method is used.

[0080] Here, a carrier for moving the thin film formation inhibitor and the thin film precursor compound onto the substrate is used. The rear gas or dilution gas is argon (Ar), nitrogen (N2), or helium (He). One or more mixed gases selected from the following may be used, but are not limited thereto.

[0081] As the purge gas in this description, for example, an inert gas can be used, and is preferably used. Alternatively, the above-mentioned carrier gas or diluent gas can be used.

[0082] Next, a reaction gas is supplied. The reaction gas is generally used in the technical field to which the present invention pertains. There is no particular limitation as long as the reaction gas is usable, and preferably, a reducing agent, a nitriding agent, or an oxidizing agent is used. The reducing agent may react with the thin film precursor compound adsorbed on the substrate to form a metal In the case of the nitriding agent, a thin film of a metal nitride is formed, and in the case of the oxide, a thin film of a metal nitride is formed. In the case of a chemical agent, a metal oxide thin film is formed.

[0083] Preferably, the reducing agent is ammonia gas (NH3) or hydrogen gas (H2). The nitriding agent may be nitrogen gas (N2) and the oxidizing agent may be H2O , H2O2, O2, O3, and N2O.

[0084] Next, an inert gas is used to purge the remaining unreacted reactant gas. Not only the excess reaction gas but also the by-products formed can be removed together.

[0085] As described above, the step of adsorbing the thin film formation inhibitor on the substrate, A step of purging the agent, a step of adsorbing the thin film precursor compound on the substrate, and a step of removing the unadsorbed thin film precursor compound from the substrate. The steps of purging the composition, supplying a reactant gas, and purging the remaining reactant gas are performed in a manner similar to the steps of: The unit cycle is repeated to form a thin film of a desired thickness. This can be done.

[0086] The unit cycle is, for example, 100 to 1000 times, preferably 100 to 500 times. More preferably, it may be 150 to 300 times. Within this range, the desired thin film characteristics can be obtained. This has the effect of allowing the properties to be expressed well.

[0087] FIG. 1 is a process diagram for explaining a conventional ALD process, and FIG. 2 is a process diagram for explaining the ALD process of the present invention. FIG. 1 is a process diagram illustrating an ALD process according to an embodiment. As in the LD process, the growth inhibitor for thin film formation according to the present invention is In order to achieve this, a thin film precursor compound (e.g., TiCl4) is first adsorbed on the substrate. If the surface is not protected, it will react with reactive gas (e.g., NH3) and form Process by-products such as HCl remain on the thin film (e.g., TiN) and cause corrosion and deterioration. However, as shown in FIG. For the growth inhibitor (TSI), the thin film precursor compound (e.g., T iCl4) is first adsorbed to protect the surface of the substrate (Surface Pr In the case of SP, when forming a thin film (e.g., TiN), the reaction gas is By-products of the process, such as HCl generated by reaction with benzene (e.g., NH3), are The long-term removal of the inhibitor prevents corrosion and deterioration of the substrate, and The thin film growth rate is appropriately reduced, and the step coverage and the uniformity of the thin film thickness are also improved.

[0088] The semiconductor substrate of the present invention is characterized by being manufactured by the thin film forming method of the present substrate, In such a case, it is necessary to appropriately reduce the thin film growth rate by suppressing side reactions and to reduce the process by-products in the thin film. Removing the material prevents corrosion and deterioration and improves step coverage. In addition, the uniformity of the thin film thickness is significantly improved.

[0089] The produced thin film preferably has a thickness of 20 nm or less and a specific resistance of 0.1 to 1.0 μm. 400μΩ·cm, halogen content is 10,000ppm or less, and step coverage is Within this range, the film has excellent performance as a diffusion barrier and prevents corrosion of metal wiring materials. However, the present invention is not limited to this.

[0090] The thin film has a thickness of, for example, 5 to 20 nm, preferably 10 to 20 nm, and more preferably The thickness may be 15 to 18.5 nm, and more preferably 17 to 18.5 nm. Within this range, there is an effect of excellent thin film properties.

[0091] The thin film has a specific resistance of, for example, 0.1 to 400 μΩ·cm, preferably 50 to 400 μΩ·cm. Ω·cm, and more preferably 100 to 300 μΩ·cm. , and has the effect of providing excellent thin film properties.

[0092] The thin film preferably has a halogen content of 9,000 ppm or less or 1 to 9,0 00 ppm, more preferably 8,500 ppm or less or 100 to 8,500 ppm, More preferably, it is 8,200 ppm or less or 1,000 to 8,200 ppm. Within this range, the thin film characteristics are excellent while the corrosion of the metal wiring material is reduced. This has the effect of:

[0093] As an example, the thin film has a step coverage of 80% or more, preferably 90% or more, and more preferably Within this range, even thin films with complex structures can be easily deposited on a substrate. This has the advantage that it can be applied to next-generation semiconductor devices.

[0094] The thin film formed may be, for example, a TiN or TiO2 thin film.

[0095] In the following, preferred embodiments and drawings are presented to aid in understanding the present invention. The examples and drawings are merely illustrative of the invention and are not intended to be limiting unless otherwise specified, and are not intended to be limiting unless otherwise specified. Variations and modifications will be apparent to those skilled in the art, and such variations and modifications are contemplated herein. It is understood that all such modifications and variations are within the scope of the appended claims.

[0096] [Example] <Examples 1 to 3 and 6> The growth inhibitor for thin film formation shown in Table 1 below and TiCl4 as a thin film precursor compound The prepared thin film growth inhibitor was placed in a canister and left at room temperature. Using a LMFC (Liquid Mass Flow Controller), 0. The mixture was fed to a vaporizer heated to 150°C at a flow rate of 0.05g / min. Vaporized thin film growth inhibitor was injected into the deposition chamber with the substrate loaded for 1 second. After this, argon gas was supplied at 5000sccm for 2 seconds to perform argon purging. The pressure in the reaction chamber was controlled at 2.5 Torr. The TiCl4 was placed in a separate canister and heated at room temperature in a LMFC (Liquid Mass Chromatograph). Flow Controller) was used, and the flow rate was 0.05g / min. The TiCl4 vaporized in the vapor phase in the vaporizer was fed to a separate heated vaporizer. After inserting the sample into the deposition chamber, argon gas was supplied at 5000sccm for 2 seconds. The reaction chamber was purged with argon at 2.5 Torr. Next, 1000 sccm of ammonia was introduced into the reaction chamber as a reactive gas for 3 seconds. After the injection, argon purging was carried out for 3 seconds. This process was repeated 200 times to obtain the self-limiting atomic layer T An iN thin film was formed.

[0097] [Table 1]

[0098] <Example 4> The growth inhibitor for thin film formation shown in Table 1 above and TiCl4 as a thin film precursor compound were used. The prepared thin film growth inhibitor was placed in a canister and incubated at room temperature for 10 min. Using MFC (Liquid Mass Flow Controller), The TiCl4 was fed at a flow rate of 5 g / min into a vaporizer heated to 150°C. Put it in a separate canister and heat it in LMFC (Liquid Mass Flow C) at room temperature. A flow rate of 0.05 g / min was applied to another sample heated to 150°C using a flowmeter. The mixture was then fed to a vaporizer.

[0099] TiCl4 vaporized in the vapor phase by the vaporizer was introduced into the deposition chamber for 1 second, and then argon Argon purging was performed by supplying gas at 5000 sccm for 2 seconds. The pressure in the chamber was controlled at 2.5 Torr. Next, the thin film was formed by vaporizing the gas into the vapor phase in the vaporizer. The growth inhibitor was injected into the deposition chamber with the substrate loaded for 1 second, and then the argon was added. Argon purging was performed by supplying argon gas at 5000 sccm for 2 seconds. The pressure in the reaction chamber was controlled at 2.5 Torr. Next, ammonia was added as a reactive gas. 1000 sccm was introduced into the reaction chamber for 3 seconds, followed by argon purging for 3 seconds. In this case, the substrate on which the metal thin film was to be formed was heated to 440 to 500°C. This process was repeated 200 times to form a TiN thin film, which is a self-limiting atomic layer.

[0100] <Example 5> The growth inhibitors for thin film formation and the thin film precursor compounds listed in Table 1 were used to prepare Si2Cl6. The prepared growth inhibitor for thin film formation was placed in a canister and heated at room temperature in LMFC( Liquid Mass Flow Controller) was used to measure the volume of the sample at 0.05g / m The Si2Cl6 was supplied to a vaporizer heated to 150 °C at a flow rate of 1000 g / cm. canister and stored in LMFC (Liquid Mass Flow Control) at room temperature. Another vaporizer was heated to 150°C using a vaporizer roller at a flow rate of 0.05g / min. was supplied to the vessel.

[0101] The substrate is loaded with the growth inhibitor for thin film formation vaporized into the vapor phase by the vaporizer for 2 seconds. After placing the sample in the deposition chamber, argon gas was supplied at 5000sccm for 2 seconds. The pressure in the reaction chamber was controlled at 2.5 Torr. Next, Si2Cl6 vaporized into the vapor phase by the vaporizer was injected into the deposition chamber for 1 second. After that, argon gas was supplied at 5000sccm for 2 seconds to perform argon purging. At this time, the pressure in the reaction chamber was controlled at 2.5 Torr. Next, the reactive gas and Then, 1000 sccm of ammonia was introduced into the reaction chamber for 3 seconds, and the reactor was heated at 200 W. Then, argon purging was performed for 3 seconds. During this time, a thin metal film was formed. The substrate was heated to 460° C. This process was repeated 300 times to obtain a self-limiting A thin SiN film was formed as an atomic layer.

[0102] <Comparative Example 1> In Example 1, no growth inhibitor was used for thin film formation, and as a result, The same as in Example 1, except that the step of purging the growth inhibitor for forming the thin film was omitted. A TIN thin film was formed on the substrate by the above method.

[0103] <Comparative Examples 2 and 3> In Example 1, the thin film growth inhibitor has a bond dissociation energy of 350 kJ / mol Using n-butyl chloride and 2-chloro propane exceeding A TIN thin film was formed on the substrate in the same manner as in Example 1, except that the TIN thin film was formed on the substrate in the same manner as in Example 1.

[0104] <Comparative Example 4> In Example 5, no growth inhibitor for thin film formation was used, and as a result, The same procedure as in Example 6 was carried out, except that the step of purging the growth inhibitor for thin film formation was omitted. A thin SiN film was formed on the substrate by this method.

[0105] [Experimental Example] 1) Evaluation of deposition (deposition) As shown in Table 2 below, tert-butyl bromide Example 1 in which ide) was used as a growth inhibitor for thin film formation and Comparative Example 1 in which it was not included As a result, the deposition rate was 0.19 Å / cycle, which was higher than that of Comparative Example 1. The deposition rate was reduced by more than 40% when the deposition rate was increased. It was confirmed that the deposition rate was similar to that of the thin film forming method according to the present invention. Instead of growth inhibitors, n-butyl chloride (n-butyl chloride), which has a high bond dissociation energy, was used. chloride and 2-chloropropane, respectively. It was confirmed that the deposition rates of Comparative Examples 2 and 3 used in this study were the same as those of Comparative Example 1. Here, the decrease in deposition rate means changing the CVD deposition characteristics to ALD deposition characteristics. Therefore, it can be used as an indicator of improvement in step coverage characteristics.

[0106] In the case of a growth inhibitor for thin film formation with a bond dissociation energy of less than 50 kJ / mol, It is stable and not easy to use in deposition processes, and the bond dissociation energy is 350 kJ / mo In the case of a growth inhibitor for forming a thin film of more than 1 mm, the concentration of impurities such as carbon in the thin film may increase. do.

[0107] In addition, to confirm whether the same effect can be achieved with a SiN thin film, the following Table 2 was used. If we compare Example 5 with Comparative Example 4, the results are that Example 5 is better than Comparative Example 4. In comparison, the deposition rate was reduced by more than 10%, from 0.29 Å / cycle to 0.32 Å / cycle. It can be seen that the

[0108] FIG. 7 shows SIMS analysis results for the SiN thin films produced in Example 5 and Comparative Example 4. The graph on the right shows that Example 5 is rough compared to Comparative Example 4, which shows the graph on the left. It was confirmed that Cl was significantly reduced in all cases.

[0109] In addition, referring to Table 2 below, tert-butyl iodide (tert-butyl i odide) as a growth inhibitor for thin film formation, This is an example in which the growth inhibitor for thin film formation was supplied after argon gas purging. In the case of Example 4, the deposition rate was 0.5 times faster than that of Comparative Example 1, which did not use a growth inhibitor for thin film formation. The deposition temperature was increased by 50 When the temperature was raised to 0°C, the increase was confirmed to be nearly 16%, up to 0.37 Å / cycle. came.

[0110] In Example 4, the deposition rate is rather increased compared to Comparative Example 1, but this is different from the prior art. It was predicted that increasing the deposition rate would reduce impurities rather than increase them. An unpredictable phenomenon occurred and was linked to the through-put aspect. In that case, we could see that it offers another major advantage.

[0111] [Table 2]

[0112] 2) Impurity reduction properties The results are shown in Table 1. The impurities of the TiN thin films deposited in Examples 1 to 5 and Comparative Examples 1 to 2 were reduced. In order to compare the reduction characteristics, i.e., the reduction characteristics of process by-products, SIMS analysis was performed. The results are shown in Table 4 and Figures 3 and 4. The Cl reduction rate (%) was calculated using the following formula 2. I calculated it.

[0113] [Formula 2] JPEG2025072426000004.jpg20162

[0114] [Table 3]

[0115] *Reference thickness of sample thin film: 10 nm

[0116] As shown in Table 3, Examples 1 to 5 using the growth inhibitor for thin film formation according to the present invention The Cl intensity was lower than that of Comparative Examples 1 and 2, which did not use this compound. It was confirmed that the amount of impurities was significantly reduced, and that the material has excellent impurity reduction properties.

[0117] In addition, when comparing Example 3 and Example 4, the process method of Example 4 is more effective in reducing impurities. It was found to be extremely beneficial for both sexes.

[0118] 3 and 4 show the by-products of the process according to the deposition temperature in Example 1 and Comparative Example 1. 1 is a graph showing the reduction characteristics of the substance, i.e., the reduction rate of Cl, The thin film according to the present invention can be obtained at all deposition temperatures when an inhibitor is used, especially in the range of 480 to 520°C. The Cl intensity was lower than when no film formation inhibitor was used. It was confirmed that there was a significant decrease.

[0119] 3) Thin film growth rate reduction rate The thin film growth rates of the TiN thin films deposited in Examples 1 to 5 and Comparative Examples 1 to 3 were measured by ellipsometry. After measuring the thickness using the Ellipsometery method, The thin film growth rate reduction rate was calculated using Equation 1 above, and the results are shown in Table 4 below.

[0120] [Formula 1] Reduction rate of thin film growth rate per cycle (%) = [( ... Thin film growth rate per cycle when no growth inhibitor for thin film formation was used Thin film growth rate per cycle / Thin film growth rate per cycle without using growth inhibitor Thin film growth rate x 100

[0121] [Table 4]

[0122] As shown in Table 4, Examples 1 to 3 using the growth inhibitor for thin film formation according to the present invention The decrease in the thin film growth rate per cycle was 10 to 4 times lower than in Comparative Example 1, in which no additive was used. It was confirmed that the results were excellent at the level of 0%. In comparison, Example 5 had a 17% decrease in thin film growth rate per cycle compared to Comparative Example 2. It was confirmed that the level of the process was excellent. In this case, when comparing Example 4 with Comparative Example 1, the deposition rate in Example 4 is rather increased compared to Comparative Example 1. However, unlike conventional technology, the impurity reduction characteristics are excellent even if the deposition rate increases, and When combined with the through-put aspect, it offers another advantage. can be provided.

[0123] 4) Step coverage characteristics The TiN thin films deposited in Example 1 and Comparative Example 1 were examined for step coverage using a TEM. The results are shown in Table 5 and Figure 5 below.

[0124] [Table 5]

[0125] As shown in Table 5, Example 1 using the growth inhibitor for thin film formation according to the present invention was It was confirmed that the step coverage rate was significantly higher than that of Comparative Example 1, which did not use the following. Referring to the TEM image in FIG. 5, the TiN thin film deposited in Example 1 (SP-TiCl4) The thickness uniformity of the top and bottom of the film is the same as that of the film deposited in Comparative Example 1 (TiCl4). It was confirmed that the conformality of the step is superior to that of the TIN thin film. Here, the top and bottom cross sections are shown in Figure 6 below. The cross section of the top surface (Top) is a point 200 nm below the top surface (Top). The cross section of the bottom surface is formed at a point 100 nm above the bottom surface. This was done.

[0126] <Reference Example 1> In Example 1, tert-butyl bromide (Te tert-butyl chloride (Tert-b The preparation was carried out in the same manner as in Example 1, except that butyl chloride was used. The process was carried out to form a TiN thin film, which is a self-limiting atomic layer, based on Example 1. Compare the impurity reduction characteristics of the deposited TiN thin film with the reduction characteristics of process by-products. SIMS analysis was performed to determine the crystal structure, and the results are shown in Table 6 below.

[0127] [Table 6]

[0128] *Standard thickness of sample thin film: 10 nm

[0129] As shown in Table 6, Example 1 using the bromide thin film growth inhibitor of the present invention However, compared to Reference Example 1, which used a chloride thin film growth inhibitor, the Cl reduction rate was higher. It was confirmed that the impurity reduction properties were superior to those of the conventional method.

[0130] 5) Thin film crystallinity FIG. 8 shows the results of Comparative Example 1 in which no growth inhibitor for thin film formation was added (Ref TiN), the growth inhibitor for thin film formation was added at a rate of 0.1 / min in Example 4 (tert-BuI (0.1 g) / min)) and in Example 4, the growth Inhibitor was added at a rate of 0.1 / min (tert-BuI (0.1g / min)) This is an XRD analysis graph for the thin film precursor compound as in Example 4. After argon purging, the growth inhibitor for tert-BuI thin film formation is adsorbed. In this case, it is confirmed that the crystal grains of the thin film become larger, i.e., the crystallinity increases. Here, the size of the crystal grains can be confirmed by the peak at the (200) position of the TiN thin film. (The larger and sharper the peak at 200, the greater the crystallinity.) The increased crystallinity has the advantage that the resistivity is significantly improved.

[0131] 6) Thin film density In Comparative Example 1, no growth inhibitor for thin film formation was added (Ref TiN), In Example 4, the growth inhibitor for thin film formation was added at a rate of 0.1 / min (tert- BuI (0.1 g / min)) and the growth inhibitor for thin film formation in Example 4 was added at 0.1 / min (tert-BuI (0.1g / min)) Based on x-ray reflectometry (XRR) analysis, the following ratios were determined: The density of the TiN thin film produced in Comparative Example 1 was 4.85 g / cm 3 However, in Example 4 The density of TiN thin films produced using tert-BuI at 0.01 g / min was The strength is 5.00g / cm 3 In Example 4, tert-BuI was used at a rate of 0.1 g / min. The density of the TiN thin film produced using this method is 5.23 g / cm 3 As in Example 4, The precursor compound was first adsorbed and purged with argon, after which the thin film formation compound of tert-BuI was It was confirmed that the density of the thin film increased significantly when a long-term inhibitor was adsorbed. Therefore, the thin film according to the present invention can effectively reduce capacitance of DRAM. Which high aspect ratio integrated structures Improves the warpage characteristics of the semiconductor device and improves the barrier metal characteristics. It has better advantages.

[0132] Therefore, the present invention provides a thin film having a density of 4.95 g / cm 3 More than 5.00g, preferably 5.00g / cm 3 The above is a specific example of 4.95 to 5.50 g / cm 3 , and preferred examples are 5.0 to 5.3g / cm 3 It is possible to provide a thin film of

[0133] 7) Carbon impurities in thin films In order to confirm the carbon impurities in the thin film, the thin films of Example 6 and Comparative Examples 2 and 3 were The film sample was subjected to XPS elemental analysis at various depths. The carbon concentration in the thin film is shown in Fig. 9, carbon was not detected in Example 6, but in Comparative Example 2 In the cases of , 3, carbon was detected at 15% and 16%, respectively.

Claims

1. The following chemical formula 1 [Chemical formula 1] AnBmXoYiZj (A is carbon or silicon, and B is hydrogen or alkyl having 1 to 3 carbon atoms. The X is the bond dissociation energy ) is a leaving group having a molecular weight of 50 to 350 KJ / mol, Y and Z are independently selected from the group consisting of oxygen, nitrogen, sulfur and fluorine. wherein n is an integer of 1 to 15, and o is one or more of the following: m is an integer of 0 to 2n+1, and i and j are integers of 0 to 3. wherein the compound is represented by Growth inhibitor for thin film formation.

2. In the formula 1, o is an integer of 1 to 5. The growth inhibitor for forming a thin film according to claim 1.

3. The compound represented by the formula 1 is preferably a branched, cyclic or aromatic compound. Signs, The growth inhibitor for forming a thin film according to claim 1.

4. The compound represented by Formula 1 is characterized in that it can be used in an atomic layer deposition (ALD) process. Let us say, The growth inhibitor for forming a thin film according to claim 1.

5. The compound represented by the formula 1 is liquid at room temperature (22° C.) and has a density of 0.8 ~1.5g / cm ３ The vapor pressure (20°C) is 1 to 300 mmHg, and the viscosity of the vapor relative to water is The solubility (25°C) is 200 mg / L or less. The growth inhibitor for forming a thin film according to claim 1.

6. The following chemical formula 1 [Chemical formula 1] AnBmXoYiZj (A is carbon or silicon, and B is hydrogen or alkyl having 1 to 3 carbon atoms. X is the bond dissociation energy is a leaving group having a molecular weight of 50 to 350 KJ / mol, Y and Z are independently selected from the group consisting of oxygen, nitrogen, sulfur, and fluorine. wherein n is an integer of 1 to 15, and o is 1. or more, m is an integer of 0 to 2n+1, and the i and j are integers of 0 to 3. The growth inhibitor for thin film formation is injected into the ALD chamber for loading. g) adsorbing the compound on the substrate surface. Thin film formation method.

7. i) The growth inhibitor for thin film formation is vaporized to form a substrate loaded in the ALD chamber. Adsorbing onto the surface of the plate; ii) initially purging the interior of the ALD chamber with a purge gas; iii) vaporizing a thin film precursor compound and depositing it on the surface of a substrate loaded in an ALD chamber; Adsorbing to a surface; iv) performing a second purge of the ALD chamber with a purge gas; v) supplying a reactant gas into the ALD chamber; and vi) tertiary purging of the inside of the ALD chamber with a purge gas. do, The thin film forming method according to claim 6.

8. i) vaporizing a thin film precursor compound onto the surface of a substrate loaded in an ALD chamber; Adsorption step; ii) initially purging the interior of the ALD chamber with a purge gas; iii) The growth inhibitor for forming the thin film is vaporized and loaded into the ALD chamber. adsorbing the polymer on a surface of the substrate; iv) performing a second purge of the ALD chamber with a purge gas; v) supplying a reactant gas into the ALD chamber; and vi) tertiary purging of the inside of the ALD chamber with a purge gas. do, The thin film forming method according to claim 6.

9. The growth inhibitor and the thin film precursor compound for forming the thin film are used in the VFC method, DLI method or L The substrate is transferred into the ALD chamber by the DS method. The thin film forming method according to claim 7 or 8.

10. The amount of the growth inhibitor and the precursor compound for forming the thin film in the ALD chamber (mg / cycle) ratio is 1:1.5 to 1:20; The thin film forming method according to claim 7 or 8.

11. The thin film formation method is carried out by using a thin film growth rate (Å / c) per cycle calculated by the following Equation 1: The decrease rate of the cycle is -5% or less, The thin film forming method according to claim 7 or 8. [Formula 1] Reduction rate of thin film growth rate per cycle (%) = [( ... Thin film growth rate per cycle when no thin film growth inhibitor was used Thin film growth rate per cycle) / Thin film growth rate per cycle when no growth inhibitor for thin film formation was used Thin film growth rate x 100

12. The thin film formation method was performed using SIMS to measure the thickness of the thin film formed after 200 cycles. The strength (c / s) of residual halogen in the thin film is 10,000 or less. The thin film forming method according to claim 7 or 8.

13. The reactive gas is a reducing agent, a nitriding agent, or an oxidizing agent. The thin film forming method according to claim 7 or 8.

14. A semiconductor substrate manufactured by the thin film forming method according to claim 6.

15. The thin film thus produced has a thickness of 20 nm or less and a specific resistance of 0.1 to 400 μΩ· cm, the halogen content is 10,000 ppm or less, and the step coverage is 80% or more. Characterized in that The semiconductor substrate according to claim 14.

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