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

Abstract

To provide: a growth inhibitor for forming a thin film capable of significantly improving step coverage and thickness uniformity of the thin film even when the thin film is formed on a substrate having a complicated structure by inhibiting side reactions to reduce a thin film growth rate and removing process by-products from within the thin film; a thin film forming method using the same; and a semiconductor substrate manufactured by the same.SOLUTION: There is provided a growth inhibitor for forming a thin film, which is a compound represented by Chemical Formula 1 below: [Chemical Formula 1] AnBmXoYiZj, where A is carbon or silicon, B is hydrogen or alkyl having 1 to 3 carbon atoms, X is one or more of fluorine, chlorine, bromine, and iodine, 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 more, m is 0 to 2n+1, and I and j are integers of 0 to 3. There are also provided: a method for forming a thin film using the same; and a semiconductor substrate manufactured using the same.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 appropriately reduces the thin film growth rate by suppressing side reactions. By lowering the temperature and removing process by-products in the thin film, corrosion and deterioration are prevented, and Even when forming a thin film on a substrate with a complex structure, the step coverage is excellent. ge) and a growth inhibitor for thin film formation that greatly improves the uniformity of the thin film thickness, The present invention relates to a thin film forming method and a semiconductor substrate manufactured 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 of various thin films deposited on substrates has become more and more important. Step coverage is becoming increasingly important.

[0003] The semiconductor thin film is made of metal nitride, metal oxide, metal silicide, or the like. The films are titanium nitride (TiN), tantalum nitride (TaN), zirconium nitride (Zr N), and the thin film is generally a doped semiconductor silicon layer and an interlayer The diffusion barrier film (di) between the wiring materials aluminum (Al) and copper (Cu) However, a thin tungsten (W) film is used as a fusion barrier. When deposited on a substrate it is used as an adhesion layer.

[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. Chemical vapor deposition ALD (atomic layer deposition) is a process that utilizes surface reactions rather than processes. The yer deposition process is used, but 100% step coverage is not achieved. Problems still exist in achieving step coverage.

[0005] In addition, titanium nitride (TiN), which is a representative metal nitride, is deposited. In the case of titanium tetrachloride (TiCl4) used for the purpose, the chloride and By-products from such processes 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 device and a semiconductor substrate manufactured from the method. It is emotion. [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. By appropriately reducing the elongation rate and removing process by-products in the thin film, corrosion and degradation are prevented. It also has step coverage when forming a thin film on a substrate with a complex structure. 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 same and a semiconductor substrate manufactured using the same. do.

[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.) wherein X is one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I). and wherein 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 The symbol o is an integer of 1 or more, the symbol m is an integer of 0 to 2n+1, and the symbols i and j are integers of 0 to 3. The present invention provides a growth inhibitor for thin film formation, which is a compound represented by the formula:

[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 a growth inhibitor into an ALD chamber. and adsorbing the thin film on a surface of a loaded substrate. do.

[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 in 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 in 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] 1 is an XRD analysis graph for Comparative Example 1 in which no growth inhibitor for thin film formation was added (Ref TiN), Example 4 in which a growth inhibitor for thin film formation was added at a rate of 0.1 g / min (tert-BuI (0.1 g / min)), and Example 4 in which a growth inhibitor for thin film formation was added at a rate of 0.1 g / min (tert-BuI (0.1 g / min)). [Figure 9] 1 is a SIMS analysis graph showing the reduction rate of F (fluorine), C (carbon), and the like depending on the deposition time (Sputter Time) for Example 6 (SP-NbF5) of the present invention and Comparative Example 5 (NbF5). Here, the graph on the right is a graph in which the growth inhibitor for thin film formation of the present invention is applied, and the graph on the left is a graph for Comparative Example 5, which corresponds to a reference in which the growth inhibitor for thin film formation was not used. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The following describes the growth inhibitor for thin film formation described herein, a thin film formation method using the same, and a product made therefrom. The fabricated semiconductor substrate 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 the precursor compound is adsorbed, a halogen-substituted compound having a specific structure is added to inhibit the growth of the thin film. When the agent is first adsorbed, the growth rate of the thin film formed after deposition is significantly reduced. The difference coverage is greatly improved, and the amount of residual halides as process by-products is greatly reduced. In addition, it was confirmed that the surface of the substrate loaded inside the ALD chamber was The thin film precursor compound is first adsorbed, and then a halogen-substituted compound having a specific structure is adsorbed to inhibit the growth of the thin film. When adsorbed as an agent, contrary to expectation, it behaved as a film quality improver and The film growth rate was increased, and residual halides as process by-products were significantly reduced, resulting in a thin The results confirmed that the density and resistivity of the film were significantly improved. As a result of this research, the present invention was completed.

[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 one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I). Y and Z are independently selected from oxygen, nitrogen, sulfur, and fluorine (F). are not identical to each other, and n is an integer of 1 to 15. wherein o is an integer of 1 or more, m is an integer of 0 to 2n+1, and i and j are an integer of 0 to 3. ) In such a case, the compound is characterized by suppressing side reactions during thin film formation. This reduces the film growth rate and also removes process by-products within the film, preventing corrosion and deterioration. The step coverage (st) is excellent even when a thin film is formed on a substrate with a complex structure. The effect of significantly improving the ep coverage and the uniformity of the thin film thickness is do.

[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 The integer is 4 to 6. Within this range, the effect of removing process by-products is large and the step coverage is excellent. can be.

[0024] In the above formula 1, X is preferably one of bromine (Br) and iodine (I). More preferably, it may be iodine. In this case, it is possible to suppress side reactions and to improve the process. The higher the concentration, the more effectively the by-products can be removed.

[0025] In the above formula 1, o is preferably an integer of 1 to 5, more preferably an integer of 1 to 3. and more preferably, 1 or 2. Within this range, the deposition rate reduction effect This has the advantage of being more effective in improving step coverage.

[0026] 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.

[0027] The Y and Z are preferred examples, and each of them is independently oxygen, nitrogen, and fluorine. and are not identical to each other.

[0028] In a preferred embodiment, i and j are not both 0, and in a specific embodiment, they are integers from 1 to 3. It's possible.

[0029] 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 butane), 1-iodo-1-isopropylcyclohexane (1-iodo-2-meth yl propane), 1-iodo-1-isopropylcyclohexane isopropylcyclohexane), 1-iodo-4-nitrobenzene (1-iod o-4-nitrobenzene), 1-iodo-4-methoxybenzene (1-iodo-4 -methoxybenzene), 1-iodo-2-methylpentane ethylpentane), 1-iodo-4-trifluoromethylbenzene (1-iodo- 4-trifluoromethylbenzene), tert-butyl iodide (tert -butyl iodide) and 1-methyl-1-iodocyclohexane (1-methy l-1-iodocyclohexane), 1-bromo-4-chlorobenzene (1-bromo o-4-chlorobenzene), 1-bromopropane, 1-bromobutane 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromo-2-methylpropane omo-2-methylpropane, 1-bromooctane nce), 1-bromonaphthalene, 1-bromo-4-io 1-bromo-4-iodobenzene and 1-bromo-4-nitrobenzene One selected from the group consisting of 1-bromo-4-nitrobenzene In this case, the effect of removing process products is large, and the effect of improving step coverage and film quality is improved. Excellent results.

[0030] The compound represented by Formula 1 is preferably used in the process of atomic layer deposition (ALD). In this case, the thin film precursor compound is not prevented from adsorbing on the substrate as a growth inhibitor. Effective protection of the surface and effective removal of process by-products. This has the advantage that

[0031] The compound represented by the formula 1 is preferably liquid at room temperature (22° C.) and has a density of 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 its solubility in water (25°C) is 20 Within this range, the step coverage, the thickness uniformity of the thin film, and This has the effect of improving the film quality.

[0032] 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) can be 160mg / L or less. Among them, it has excellent effects on step coverage, thin film thickness uniformity, and film quality improvement.

[0033] 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

[0034] (The above A is carbon or silicon, and the above B is hydrogen or an alkyl group having 1 to 3 carbon atoms.) wherein X is one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I). and Y and Z are independently selected from oxygen, nitrogen, sulfur, and fluorine. and n is an integer of 1 to 15. wherein o is an integer of 1 or more, m is an integer of 0 to 2n+1, and i and j are an integer of 0 to 3. The growth inhibitor for thin film formation represented by the formula (1) is injected into the ALD chamber to form a load cell. The method includes a step of adsorbing the compound on a loaded substrate surface. In such a case, the side reaction is suppressed, the deposition rate is slowed down, and the thin film growth rate is reduced. In addition, by removing process by-products in the thin film, it is possible to form thin films on substrates with complex structures. Even when a film is formed, the step coverage and the uniformity of the thin film thickness are required. This has the effect of greatly improving unity.

[0035] The step of adsorbing the growth inhibitor for thin film formation on the surface of the substrate includes adsorbing the growth inhibitor for thin film formation on the surface of the substrate. The feeding time of the growth inhibitor is preferably 1 to 20 minutes per cycle. 10 seconds, more preferably 1 to 5 seconds, even more preferably 2 to 5 seconds, and even more preferably 2 Within this range, the thin film growth rate is low, and the step coverage and economy are excellent. There are advantages.

[0036] 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.

[0037] In a preferred embodiment of the thin film forming method, the method further comprises the steps of: i) vaporizing a growth inhibitor for forming the thin film; and adsorbing the A to a surface of a substrate loaded in an ALD chamber; iii) purging the inside of the LD chamber with a purge gas; and iii) vaporizing the thin film precursor compound. iv) adsorbing the compound on a surface of a substrate loaded in an ALD chamber; v) purging the inside of the ALD chamber with a purge gas; and vi) tertiary purging the interior of the ALD chamber with a purge gas. In such a case, the thin film growth rate is appropriately reduced, and the thin film formation Even if the deposition temperature is sometimes high, the process by-products generated are effectively removed, and the resistivity of the thin film is The advantage is that the step coverage is significantly improved. .

[0038] 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 compound on a surface of a substrate loaded in an ALD chamber; 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 iv) vaporizing the growth inhibitor for forming a thin film. and adsorbing the A to a surface of a substrate loaded in an ALD chamber; iv) v) purging the inside of the LD chamber with a purge gas; supplying a reaction gas; and vi) tertiary purging the interior of the ALD chamber with a purge gas. In such a case, the thin film growth rate is increased, and the thin film is formed. Even at high deposition temperatures, the process by-products that are generated are effectively removed, allowing the thin films to be The advantages are that the resistivity of the film is reduced and the film density and crystallinity are greatly improved.

[0039] The growth inhibitor for forming the thin film and the thin film precursor compound are preferably VFC type, DL type The ALD chamber can be transported in the LDS or LDS manner, and more preferably in the LDS manner. It is transferred into the ALD chamber using the DS method.

[0040] The growth inhibitor and the precursor compound for forming the thin film are introduced into the ALD chamber. The ratio of input amounts (mg / cycle) may preferably be 1:1.5 to 1:20. More preferably, the ratio is 1:2 to 1:15, and even more preferably, the ratio is 1:2 to 1:12. More preferably, the ratio is 1:2.5 to 1:10. Within this range, the thinning ratio per cycle is The reduction rate of the film growth rate (GPC) is high, and the effect of reducing process by-products is great.

[0041] The thin film precursor compound is a thin film precursor compound typically used in ALD (atomic layer deposition). There is no particular limitation as long as the compound is a metal film precursor compound or a metal oxide film precursor compound. a compound, a metal nitride film precursor compound, or a silicon nitride film precursor compound, the metal being 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:

[0042] As an example, the thin film precursor compound containing niobium as the metal is preferably NbF5. In this case, the effect of the present invention is advantageously exhibited. be.

[0043] 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 carbonyl compounds and substituted or unsubstituted cyclopentadienyl metal compounds. The present invention may be, but is not limited to, one or more of the above.

[0044] As a specific example, the metal film precursor, the metal oxide film precursor, and the metal nitride film precursor are These are tetrachlorotitanium and tetrachloroja, respectively. Tetrachlorogemanium, tetrachlorotine lorotin, tris(isopropyl)ethylmethylaminogermanium (tris( isopropyl)ethylmethyl aminogermanium), tetraethyl Tetraethoxylgermanium, tetramethyl tin, tetraethyl tin in), bisacetylacetonate tin ), trimethylaluminum, tetrakis(dimethylamino) Tetrakis(dimethylamino)germanium anium, bis(n-butylamino)germanium o) germanium, tetrakis(ethylmethylamino)tin (ethylmethylamino) tin), tetrakis(dimethylamino)tin ( tetrakis(dimethylamino)tin), Co2(CO)8(dicobata dicobalt octacarbonyl), Cp2Co( Biscyclopentadienylcobalt lt), Co(CO)3(NO) (tricarbonyl nitrosyl cobalt; cobalt t ricarbonyl nitrosyl), and CpCo(CO)2 (cyclopentadiene Cobalt dicarbonyl cyclopen The alkyl group may be, but is not limited to, one or more selected from the group consisting of aryl, aryl tadienyl, and the like. It is not possible.

[0045] 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)3、(NEt2)Si(NH i Bu)3、(NEt 2)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(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 nBu2)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) 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 nBu)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(NH i 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<h2 style=";text-align:left;direction:ltr">Pr<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> )2、Si(<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)2, Si(<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<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> )2、Si(<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> BuNCH2CH2N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Bu(2、Si()<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<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> )2、Si(HNCHCHNH)2、Si(MeNCHCHNMe)2、Si(EtNC)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> HCHNEt)2, Si(<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> PrNCHCHN<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Pr)2, Si(<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"> <h2 style=";text-align:left;direction:ltr"> Pr)2, Si(<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(2、Si()<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)2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> Si(<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)2、(HNCHCHNH)Si(HNCH2CH2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> NH)、(MeNCHCHNMe)Si(MeNCH2CHNMe)、(EtNCHCH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> NEt)Si(EtNCH2CH2NEt)、(<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> PrNCHCHN<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Pr)Si(<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> P<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> rNCH2CH2N<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Pr)、(<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)Si(<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> PrNCH2CH<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"> Pr)、(<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(Si()<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)、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (<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(Si()<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> BuNCH2CH2N<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Bu)、(<h2 style=";text-align:left;direction:ltr"> t<h2 style=";text-align:left;direction:ltr">BUNCH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CHN<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> Bu(Si()<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)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(Bu)2Si( t BuNCHCHN t (Bu)、( i PrNCH2CH2N i P (Pr)Si(NHMe)2、( i PrNCH2CH2N i (Pr)Si(NHEt)、( i P PrNCH2CH2N 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 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 and i PrNCHCHN i (Pr)Si(NH t selected from the group consisting of one or more of (Bu)2 The above may be included, but is not limited to these.

[0046] 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.

[0047] In one preferred embodiment, the thin film precursor compound may be titanium tetrahalide.

[0048] The titanium tetrahalide can be used as a metal precursor for a thin film-forming composition. can.

[0049] The titanium tetrahalides include, for example, TiF4, TiCl4, TiBr4, and TiI4, for example, Ti From an economical point of view, Cl4 is preferable, but the present invention is not limited thereto.

[0050] 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.

[0051] In one example, the thin film precursor compound may be mixed with a non-polar solvent and then introduced into the chamber. In this case, the viscosity and vapor pressure of the thin film precursor compound can be easily adjusted. There is.

[0052] 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.

[0053] In a more preferred embodiment, the non-polar solvent is a C1 to C10 alkane, or C3 to C10 cycloalkanes, and are preferred. or C3 to C10 cycloalkanes, in which case the reaction It has the advantages of low viscosity and solubility, making moisture control easy.

[0054] In this description, C1, C3 etc. refer to carbon numbers.

[0055] 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. It is not limited.

[0056] The non-polar solvent preferably has a solubility in water (at 25° C.) of 200 mg / L or less, for example. or 50 to 200 mg / L, more preferably 135 to 175 mg / L. It has the advantage of being less reactive to thin film precursor compounds and easier to control moisture. .

[0057] The solubility in this description is measured by a method or standard commonly used in the technical field to which the present invention pertains. As long as the measurement is based on the above, there is no particular limitation. For example, a saturated solution is measured by HPLC. It is possible.

[0058] The non-polar solvent is preferably a total of the thin film precursor compound and the non-polar solvent. The content may be 5 to 95% by weight, and more preferably 10 to 90% by weight. It is more preferable that the content of the cellulose acetate is 40 to 90% by weight, and most preferably that the content of the cellulose acetate is 70 to 90% by weight. It may contain up to 90% by weight.

[0059] If the content of the non-polar solvent exceeds the upper limit, impurities may be generated. , the resistance and the number of impurities in the thin film increase, and the content of the organic solvent is When the amount is less than 1000g, the effect of improving the step coverage by adding a solvent and the effect of reducing the amount of chlorine (Cl) However, there is a drawback in that the effect of reducing impurities such as on is small.

[0060] In the thin film forming method, for example, the thin film per cycle is calculated by the following formula 1. The decrease in growth rate (Å / Cycle) is -5% or less, preferably -10% or less, more preferably Preferably, it is −20% or less, more preferably −30% or less, and even more preferably −4 0% or less, and most preferably -45% or less. Within this range, the step coverage and the film thickness Excellent uniformity.

[0061] [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

[0062] 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 8,000 or less, 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. .

[0063] 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.

[0064] 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.

[0065] 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. The deposition temperature is preferably in the range of 400 to 500° C. Within this range, a thin film with excellent film quality can be grown while realizing the ALD process characteristics. This has the effect of making the

[0066] 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 can be preferably in the range of 0.5 to 5 Torr, and most preferably in the range of 1 to 5 Torr. The deposition pressure is in the range of 3 Torr, and within this range, a thin film of uniform thickness can be obtained. There is an effect to be gained.

[0067] 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 can be done.

[0068] 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.

[0069] The present invention also provides a thin film manufacturing apparatus capable of implementing the thin film manufacturing method, comprising: D chamber, the first vaporizer that vaporizes the growth inhibitor for thin film formation, the growth inhibitor for thin film formation vaporized A first delivery means for delivering an inhibitor into the ALD chamber, a second delivery means for vaporizing a Ti-based thin film precursor, A vaporizer and a second transfer means for transferring the vaporized Ti-based thin film precursor to the ALD chamber. The present invention can include a thin film manufacturing apparatus including the vaporizer and the transport means. There is no particular limitation as long as the vaporizer and transport means are those commonly used in the technical field.

[0070] 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.

[0071] The substrate may include a semiconductor substrate such as a silicon substrate, silicon oxide, or the like.

[0072] The substrate may further have a conductive or insulating layer formed thereon.

[0073] 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.

[0074] After that, the prepared thin film formation inhibitor is injected into the vaporizer, and then it is converted into a vapor phase and evaporated. 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 (purged). rging).

[0075] Next, the prepared thin film precursor compound or its mixture with 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 a substrate, and then the unadsorbed thin film is removed. Purging the composition.

[0076] 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. Transfer liquids using either the Liquid Phase Flow Control (VFC) or Liquid Phase Flow Control (LMFC) methods. The Liquid Delivery System (LDS) can be used. Preferably, the LDS method is used.

[0077] 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.

[0078] In this description, as an example of the purge gas, an inert gas may be used. Preferably, the above-mentioned carrier gas or diluent gas can be used.

[0079] 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 thin metal oxide film is formed.

[0080] 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.

[0081] 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.

[0082] 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. Purging the composition, supplying a reactant gas, and purging residual reactant gas. Each step is regarded as a unit cycle, and the unit cycle is repeated to form a thin film of a desired thickness. It can be repeated.

[0083] 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.

[0084] 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 with the LD process, the growth inhibitor for thin film formation according to the present invention Before adsorbing a thin film precursor compound (e.g., TiCl4), If the protective layer is not used, the thin film formed by reaction with the reactive gas (e.g., NH3) may be The film (e.g. TiN) may contain process by-products such as HCl, which may cause corrosion and deterioration. However, as shown in FIG. 2, the thin film forming method of the present invention For the growth inhibitor (TSI), a thin film precursor compound (e.g., Ti Before adsorbing Cl4, the substrate surface was first protected by adsorbing it (Surface Protect In the case of SP, when forming a thin film (e.g., TiN), the reaction gas ( For example, the process by-product HCl generated by reaction with NH3) can be used as a compound for thin film formation. By removing the inhibitor together with the substrate, corrosion and deterioration of the substrate can be prevented, and the The thin film growth rate is appropriately reduced, and step coverage and thin film thickness uniformity are also improved.

[0085] 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. By removing the material, corrosion and deterioration are prevented, and step coverage is improved. ge) and the uniformity of the thin film thickness are excellent.

[0086] 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.

[0087] 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 preferably 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.

[0088] The thin film has a resistivity of, for example, 0.1 to 400 μΩ·cm, preferably 50 to 40 0 μΩ·cm, and more preferably 100 to 300 μΩ·cm. Within this range, there is an effect of excellent thin film characteristics.

[0089] The thin film preferably has a halogen content of 9,000 ppm or less, or 1 to 9, 000 ppm, more preferably 8,500 ppm or less or 100 to 8,500 ppm More preferably, the concentration 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 making the

[0090] 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.

[0091] The thin film formed may be, for example, a TiN or TiO2 thin film.

[0092] 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.

[0093] [Example] <Examples 1 to 3> The growth inhibitor for thin film formation shown in Table 1 below and TiCl4 as a thin film precursor compound were used. The growth inhibitors for thin film formation were 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 growth inhibitor for thin film formation was applied to the deposition chamber with the substrate loaded for 1 second. After this, argon gas was supplied at 5000sccm for 2 seconds to During this process, 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 Metal FC). Flow Controller) at a flow rate of 0.05 g / min. The TiCl4 vaporized in the vapor phase in the vaporizer was fed to a separate vaporizer heated to ℃. After being placed in the deposition chamber for 1 second, argon gas is supplied at 5000sccm for 2 seconds. The pressure in the reaction chamber was controlled to 2.5 Torr. Next, 1000 sccm of ammonia was supplied as a reactive gas for 3 seconds to the reaction chamber. After the sample was placed in the oven, argon was purged for 3 seconds. The plate was heated to 460° C. This process was repeated 200 times to obtain a self-limiting atomic layer. A thin TiN film was formed.

[0094] [Table 1]

[0095] <Example 4> The growth inhibitor for thin film formation shown in Table 1 and TiCl4 as a thin film precursor compound were used. The prepared growth inhibitor for thin film formation was placed in a canister and heated at room temperature in LMF. Using C (Liquid Mass Flow Controller), 0.05g The TiCl4 was supplied to a vaporizer heated to 150°C at a flow rate of 100 / min. canister and stored in LMFC (Liquid Mass Flow Control) at room temperature. A separate gas heated to 150°C was used at a flow rate of 0.05g / min. The mixture was then fed to the catalysis device.

[0096] TiCl4 vaporized in the vapor phase by the vaporizer was introduced into the deposition chamber for 1 second, and then the TiCl4 was cooled by argon. Argon gas was supplied at 5000 sccm for 2 seconds to perform argon purging. The pressure in the chamber was controlled at 2.5 Torr. Next, the thin-film-type ZnO was evaporated to the vapor phase in the vaporizer. The growth inhibitor was injected into the deposition chamber with the substrate loaded for 1 second, followed by Al. Argon gas was supplied at 5000 sccm for 2 seconds to perform argon purging. The pressure in the reaction chamber was controlled at 2.5 Torr. 1000 sccm of argon was introduced into the reaction chamber for 3 seconds, and then argon was purged 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 that is a self-limiting atomic layer.

[0097] <Example 5> The growth inhibitor for thin film formation listed in Table 1 and Si2Cl6 as a thin film precursor compound The prepared thin film growth inhibitor was placed in a canister and left at room temperature. 0.0 using LMFC (Liquid Mass Flow Controller) The Si2Cl6 was fed to a vaporizer heated to 150°C at a flow rate of 5 g / min. 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.

[0098] The growth inhibitor for thin film formation vaporized into the vapor phase by the vaporizer is applied to the substrate for 1 second. After placing the sample in the deposition chamber, argon gas was supplied at 5000 sccm for 2 seconds. The reaction chamber was purged with argon by purging with argon. At this time, the pressure in the reaction chamber was set to 2.5 Torr. Next, the Si2Cl6 vaporized into the vapor phase by the vaporizer was placed in the deposition chamber for 1 second. After that, 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. 1000 sccm of ammonia gas was introduced into the reaction chamber for 3 seconds, and then 20 Plasma treatment was performed at 0 W. Then, argon purging was performed for 3 seconds. The substrate on which the thin film was to be formed was heated to 460°C. This process was repeated 300 times. A SiN thin film, which is a self-limiting atomic layer, was formed.

[0099] <Example 6> In Example 1, tert-butyl chloride (tert-butyl chloride) was used as a growth inhibitor for thin film formation. t-butyl chloride) as a thin film precursor compound and NbF5 as a thin film precursor compound. The same method as in Example 1 was used, except that the vaporization was performed using the VFC method instead of the LDS method. A self-limiting atomic layer NbN thin film was formed.

[0100] <Comparative Example 1> In Example 1, no growth inhibitor was used for thin film formation, and as a result, The same procedure as in Example 1 was carried out except that the step of purging the growth inhibitor for thin film formation was omitted. A thin TIN film was formed on the substrate by this method.

[0101] <Comparative Examples 2 and 3> In Example 1, pentane (Pe) was used instead of the growth inhibitor for thin film formation listed in Table 1. Except for using ntane or cyclopentane, A TIN thin film was formed on a substrate in the same manner as in Example 1.

[0102] <Comparative Example 4> In Example 5, no growth inhibitor was used for thin film formation, 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. By this method, a thin SiN film was formed on the substrate.

[0103] <Comparative Example 5> The same procedure as in Example 6 was repeated except that no growth inhibitor was added for thin film formation. A self-limiting atomic layer NbN thin film was formed in the same manner as in 6.

[0104] [Experimental Example] 1) Evaluation of deposition (deposition) As shown in Table 2 below, tert-butyl bromide Example 1 in which de) was used as a growth inhibitor for thin film formation and Comparative Example 1 in which it was not used 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 40% or more in the case of the remaining Examples 2 and 3, and Example 5. It was confirmed that the deposition rate was similar to that of the thin film forming method according to the present invention. Comparative Examples 2 and 3, in which pentane or cyclopentane was used instead of the growth inhibitor, were also used. It was confirmed that the deposition rate was the same as that of CVD deposition. This means changing the deposition characteristics to ALD deposition characteristics, so it is an indicator of improvement of step coverage characteristics. It can be utilized in this way.

[0105] In addition, to confirm whether the same effect is realized with a SiN thin film, the following Table 2 was used. If we compare Example 5 and Comparative Example 4 with reference to the results, Example 5 is superior to Comparative Example 4. In comparison, the deposition rate decreased by more than 10% from 0.29 Å / cycle to 0.32 Å / cycle. It can be seen that the

[0106] 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.

[0107] In addition, referring to Table 2 below, tert-butyl iodide dide) as a growth inhibitor for thin film formation, and the source precursor, i.e., the thin film precursor After the adsorption of the argon gas, the growth inhibitor for thin film formation was supplied. In Example 4, the deposition rate was 100% compared to Comparative Example 1, in which no growth inhibitor was used for thin film formation. The deposition temperature was increased by nearly 10% from 0.32 Å / cycle to 0.35 Å / cycle. When the temperature was raised to 500°C, the increase was confirmed to be nearly 16% to 0.37 Å / cycle. Done.

[0108] In Example 4, the deposition rate is rather increased compared to Comparative Example 1, but this is different from the prior art. That is, an increase in deposition rate does not increase impurities, but rather reduces them. Unpredictable phenomena occur and are linked to the through-put aspect. It has been found that this provides another major advantage.

[0109] [Table 2]

[0110] 2) Impurity reduction properties Based on Examples 1 to 5 and Comparative Examples 1 and 2, the impurities of the evaporated TiN thin film were 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 (%) is calculated by the following formula 2. I calculated it.

[0111] [Formula 2] JPEG2025072433000004.jpg20162

[0112] [Table 3]

[0113] *Reference thickness of sample thin film: 10 nm

[0114] As shown in Table 3, Examples 1 to 5 using the growth inhibitor for thin film formation according to the present invention The strength of Cl was significantly reduced compared to Comparative Examples 1 and 2, which did not use this, and the impurity It was confirmed that the reduction characteristics were excellent.

[0115] In addition, when comparing Example 3 and Example 4, the process method of Example 4 is superior in reducing impurities. It was confirmed that this is extremely advantageous in terms of the attenuation characteristics.

[0116] 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, i.e., Cl reduction rate, of the growth inhibitor for thin film formation according to the present invention. When using the inhibitor, the thin film according to the present invention can be obtained at all deposition temperatures, especially in the range of 480 to 520°C. The Cl intensity is greater than when no inhibitor was used. It was confirmed that the rate of decline was large.

[0117] In addition, as can be seen from FIG. 9, the growth inhibitor for thin film formation (tert-b Example of using tetyl chloride and changing the thin film precursor to Nb thin film precursor 6 is a thin film compared to Comparative Example 5 (Ref NbF5) which does not use a growth inhibitor for thin film formation. The strength (c / s) of the internal contaminants F and C has been significantly reduced, and the impurity reduction properties are excellent. More specifically, the thin film precursor NbF5 was used. Example 6 (F(c / s)=75, 197, C(c / s)=656) was Comparative Example 5 (F(c / s)=116, 925.65, C)(c / s)=1, 466), the intensities of the intramembrane contaminants F and C were reduced by 35% and 55%, respectively. It was confirmed again that the Nb thin film according to the present invention has a significantly superior impurity reduction property. I was able to do it.

[0118] 3) Decrease in thin film growth rate The thin film growth rates of the TiN thin films deposited in Examples 1 to 5 and Comparative Examples 1 and 2 were measured by ellipsometry. After measuring the thickness using the Ellipsometery method, the following results are The thin film growth rate reduction rate was calculated using Equation 1, and the results are shown in Table 4 below.

[0119] [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

[0120] [Table 4]

[0121] 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 20% compared to Comparative Example 1, in which the thin film growth rate was not used. It was confirmed that the level of the 40% was excellent. When comparing the results, the decrease in the thin film growth rate per cycle in Example 5 was 17% compared to Comparative Example 2. It was confirmed that the results were superior at the % level. In this case, when comparing Example 4 with Comparative Example 1, the deposition rate of Example 4 is rather faster than that of Comparative Example 1. However, unlike conventional technology, the impurity reduction characteristics are excellent even if the deposition speed increases, Another advantage is when it is combined with the through-put aspect. can be provided.

[0122] 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.

[0123] [Table 5]

[0124] 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, in which this was not used. Referring to the TEM image in Figure 5 below, the TiN deposited in Example 1 (SP-TiCl4) The thickness uniformity of the thin film on the top and bottom was 100%. The conformality is superior to that of the deposited TIN thin film. Here, the top and bottom cross sections are as follows: The cross section of the Top can be illustrated in FIG. 6, and the top surface (ground 200 nm below the Top) At this point, the cross section of the bottom surface is formed at a point 100 nm above the bottom surface. This was accomplished.

[0125] <Reference Example 1> In Example 1, tert-butyl bromide (TBB) was used as a growth inhibitor for thin film formation. tert-butyl chloride instead of ert-butyl bromide The same procedure as in Example 1 was used, except that butyl chloride was used instead. The process was carried out to form a TiN thin film, which is a self-limiting atomic layer, based on Example 1. The reduction of impurities, i.e., process by-products, for TiN thin films deposited by SIMS analysis was performed for comparison, and the results are shown in Table 6 below.

[0126] [Table 6]

[0127] *Reference thickness: 10 nm

[0128] 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 growth inhibitor for forming a chloride thin film, the reduction rate of Cl was higher. It was confirmed that the impurity reduction properties were superior.

[0129] 5) Thin film crystallinity FIG. 8 shows the results of Comparative Example 1 in which no growth inhibitor was added for thin film formation (Ref TiN), and 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 the thin film forming compound in Example 4 The long-term inhibitor was added at a rate of 0.1 g / min (tert-BuI (0.1 g / min) ) is an XRD analysis graph. As in Example 4, the thin film precursor compound was first adsorbed. After purging with argon, the thin film growth inhibitor of tert-BuI is adsorbed. It was confirmed that the crystal grains of the thin film became larger, i.e., the crystallinity increased. 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.

[0130] 6) Thin film density A growth inhibitor for thin film formation was not added as in Comparative Example 1 (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 in Example 4, the growth inhibitor for thin film formation was added at 0. For the one injected at a rate of 1 / min (tert-BuI (0.1g / min)), Based on X-ray reflectometry (XRR) analysis, it was determined that: 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 a rate of 0.01 g / min in 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 by this method was 5.23 g / cm 3As in Example 4, The precursor compound is first adsorbed and purged with argon, and then the tert-BuI thin film is formed. It was confirmed that the density of the thin film increased significantly when the inhibitor was adsorbed. Therefore, the thin film according to the present invention can be used for capacitance of DRAM, etc. of integrated structures having a high aspect ratio of Improved bending characteristics and better barrier metal properties This has the advantage that

[0131] Therefore, the present invention provides a thin film having a density of 4.95 g / cm 3 More than 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

Claims

[Claim 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. and X is one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I). The above, wherein Y and Z are independently selected from oxygen, nitrogen, sulfur, and fluorine. one or more selected from the group consisting of n, which are not identical to each other, and n is an integer from 1 to 15. wherein o is an integer of 1 or more, m is an integer of 0 to 2n+1, and i and j are integers of 0 to 3. The compound is represented by the formula (I). Growth inhibitor for thin film formation.

Images