Growth inhibitor for thin film formation, and thin film formation method using the same

Abstract

To provide: a growth inhibitor for thin film formation capable of suppress side reactions to lower a thin film growth rate and remove process by-products in the thin film, thereby greatly improving step coverage and thickness uniformity of a thin film even when the thin film is formed on a substrate having a complicated structure; a thin film formation method using the same; and a semiconductor substrate with the thin film formation method.SOLUTION: This invention relates to a growth inhibitor for forming a thin film, a method for forming a thin film using the same, and a semiconductor substrate prepared therefrom. More specifically, this invention relates to a growth inhibitor for forming a thin film comprising a compound represented by Chemical Formula 1 below, AnBmXo [Chemical Formula 1] (where A is carbon or silicon, B is hydrogen or a C1-C3 alkyl, X is a halogen, n is an integer of 1 to 15, o is an integer of 1 or more, and m is 0 to 2n+1.); a method for forming a thin film using the same; and a semiconductor substrate prepared 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 therefrom. More specifically, the present invention relates to a semiconductor substrate having a thin film grown on the substrate, and more particularly to a method for suppressing side reactions to appropriately reduce the thin film growth rate and to prevent the formation of a thin film in the thin film. By removing process by-products, corrosion and degradation are prevented, and thin films can be formed on substrates with complex structures. Even when forming a thin film, the step coverage and the thickness uniformity of the thin film are improved. A growth inhibitor for thin film formation that effectively improves the thin film formation method using the same and a thin film manufactured therefrom The present invention relates to a semiconductor substrate. [Background technology]

[0002] The integration density of memory and non-memory semiconductor devices is increasing day by day, and their structures are becoming more and more complex. As a result, the step coverage is becoming more and more important when depositing various thin films on a substrate. verage) is becoming increasingly important.

[0003] The semiconductor thin film is made of metal nitride, metal oxide, metal silicide, or the like. Titanium nitride (TiN), tantalum nitride (TaN), zirconium nitride (ZrN) The thin film generally includes a doped semiconductor silicon layer and an interconnect layer. The diffusion barrier film (di) between the aluminum (Al), copper (Cu), etc. used as materials 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 a thin film deposited on a substrate with favorable and uniform physical properties, it is necessary to obtain a high Therefore, chemical vapor deposition (CVD) is a method that mainly uses gas phase reactions. ALD (Al vapor deposition) is a process that utilizes surface reactions. The atomic layer deposition process is used However, there are still problems to be solved in achieving 100% step coverage.

[0005] In addition, in order to deposit titanium nitride (TiN), which is a representative of the above metal nitrides, In the case of titanium tetrachloride (TiCl4) used for this purpose, chlorides, etc., are present in the thin film produced. Process by-products remain and can cause corrosion of metals such as aluminum. 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 can be formed without corroding the interlayer wiring material. The reality is that it is necessary to develop a method for manufacturing semiconductor substrates using the method. . [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 conventional technology, the present invention provides a method for growing a thin film by suppressing side reactions. By appropriately lowering the rate and removing process by-products in the thin film, corrosion and deterioration can be prevented, and complex structures can be Even when forming a thin film on a substrate with a structure, the step coverage and A growth inhibitor for thin film formation that significantly improves the uniformity of the film thickness and the thickness of the thin film, and The present invention aims to provide a thin film formation method and a semiconductor substrate manufactured using the method.

[0009] The above and other objects of the present invention are all achieved by the present invention described below. It is possible. [Means for solving the problem]

[0010] In order to achieve the above object, the present invention provides a compound represented by the following formula 1: [C1] AnBmXo (A is carbon or silicon, and B is hydrogen or an alkyl group having 1 to 3 carbon atoms.) wherein X is a halogen, n is an integer from 1 to 15, and o is 1 or more. and m is an integer from 0 to 2n+1. Provide an inhibitor.

[0011] In addition, the present invention provides a method for forming a thin film by introducing the growth inhibitor into an ALD chamber. and adsorbing the thin film on a surface of a loaded substrate. do.

[0012] The present invention also provides a semiconductor substrate manufactured by the above-mentioned thin film formation method. Effect of the Invention

[0013] According to the present invention, the side reaction is suppressed, the deposition rate is reduced, and the thin film growth rate is appropriately reduced. By removing process by-products from the thin film, corrosion and degradation can be prevented, and the thin film can be applied to substrates with complex structures. Even when forming a thin film, the step coverage and the uniformity of the thin film thickness are required. Growth inhibitor for thin film formation that greatly improves uniformity, and thin film formation method and method using the same and a semiconductor substrate manufactured therefrom. [Brief description of the drawings]

[0014] [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 graph showing the change in film thickness with increasing ALD cycles for inventive Example 7 (SP-TiCl4) and Comparative Example 1 (TiCl4). [Figure 4] 1 is a graph showing the change in thin film thickness with the feeding amount of a thin film-forming growth inhibitor (SP) per ALD cycle for Examples 7-1 to 7-3 of the present invention and Comparative Example 1. [Diagram 5] 4 is a TEM (Transmission Electron Microscope) photograph of TiN thin films deposited in Example 1 (SP-TiCl4) and Comparative Example 1 (TiCl4). [Figure 6] 1 is a graph showing the change in deposition rate (A / cycle) with the feeding time (s) of a growth inhibitor (SP) for thin film formation per ALD cycle in Additional Example 2 of the present invention and Additional Comparative Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] 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 manufacturing a thin film using the same. The semiconductor substrate thus fabricated will now be described in detail.

[0016] The present inventors performed a thin film pre-treatment on the surface of a substrate loaded inside an ALD chamber. Before adsorbing the precursor compound, a halogen-substituted compound with a specific structure is used as a growth inhibitor. If the thin film is first adsorbed, the growth rate of the thin film formed after deposition is low, and the thin film becomes a process by-product. The residual halide residue is significantly reduced, improving step coverage. Based on this, we conducted extensive research and completed the present invention. This is what I came to do.

[0017] The growth inhibitor for thin film formation of the present invention is represented by the following chemical formula 1 [C1] AnBmXo (wherein A is carbon or silicon, and B is hydrogen or alkyl having 1 to 3 carbon atoms.) wherein X is a halogen, n is an integer from 1 to 15, and o is 1 or more. is an integer, and m is 0 to 2n+1; In such a case, it is necessary to suppress side reactions during thin film formation to reduce the thin film growth rate and to reduce the amount of by-products in the thin film process. Removal of components reduces corrosion and degradation, and allows for the formation of thin films on substrates with complex structures. Greatly improves step coverage and thin film thickness uniformity even in It has the effect of making people think.

[0018] The B is preferably hydrogen or methyl, and the n is preferably an integer of 2 to 15. more preferably an integer between 2 and 10, even more preferably an integer between 2 and 6, The preferred range is an integer from 4 to 6. Within this range, the effect of removing process by-products is high, and It has excellent differential coverage.

[0019] In the formula 1, X is, for example, one selected from the group consisting of F, Cl, Br and I. or more, preferably Cl (chlorine), in which case side reactions are suppressed to prevent process by-products It has the effect of effectively removing.

[0020] In the above formula 1, o is preferably an integer of 1 to 5, more preferably an integer of 1 or more. The deposition rate reducing effect is preferably within the range of 1 or 2. This has the advantage of being more effective in improving step coverage.

[0021] The m is preferably 1 to 2n+1, and more preferably 3 to 2n+1. Within this range, the effect of removing by-products during the process is large and the step coverage is excellent. .

[0022] The compound represented by the formula 1 is preferably a branched, cyclic or aromatic compound. Specific examples include 1,1-dichloroethane, 1,2-dichloroethane, and dichloromethane. 2-chloropropane, 1-chloropropane, 1,2-dichloropropane, 1,3-dichloropropane Chloropropane, 2,2-dichloropropane, 1-chloropentane, 2-chloropentane , 3-chloropentane, chlorocyclopentane, n-butyl chloride, tert-butyl chloride Chloride, sec-butyl chloride, isobutyl chloride, 1,2-dichlorobenzene, 1 ,4-Dichlorobenzene, Trimethylchlorosilane, Trichloropropane, 2-Chloro- One or more selected from the group consisting of 2-methylbutane, 2-methyl-1-pentane, etc. In this case, the effect of removing process by-products is large, and the advantage of excellent step coverage is obtained. be.

[0023] The compound represented by Chemical Formula 1 is preferably used in an atomic layer deposition (ALD) process, In this case, the surface of the substrate can be effectively used as a growth inhibitor without inhibiting the adsorption of the thin film precursor compound. This has the advantage of providing protection and effectively removing process by-products.

[0024] The compound represented by the formula 1 is preferably liquid at room temperature (22° C.) and has a density of 0 .8 to 1.5 g / cm 3 and the vapor pressure (20°C) is 1 to 300 mmHg. The solubility in water (25°C) is 200mg / L or less, and within this range, the step coverage is excellent. In addition, the thin film has excellent thickness uniformity.

[0025] More preferably, the compound represented by Formula 1 has a density of 0.85 to 1.3 g / mol. cm 3 The vapor pressure (20°C) is 1 to 260 mmHg, and the solubility in water ( 25℃) is 160mg / L or less, and within this range, the step coverage and thin film thickness uniformity are It has the effect of being excellent.

[0026] The thin film forming method of the present invention comprises reacting a compound represented by the following chemical formula 1 [C1] AnBmXo (wherein A is carbon or silicon, and B is hydrogen or alkyl having 1 to 3 carbon atoms.) wherein X is a halogen, n is an integer from 1 to 15, and o is 1 or more. m is an integer, and m is 0 to 2n+1. It is inserted into the ALD chamber and adsorbed onto the surface of the loaded substrate. The method is characterized by including a step of putting on the In such a case, the side reactions are suppressed, the deposition rate is slowed down, and the thin film growth rate is reduced. By removing the process by-products, even when forming a thin film on a substrate with a complex structure, Greatly improves step coverage and thin film thickness uniformity This has the effect of:

[0027] 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 for the growth inhibitor is preferably The time is preferably 1 to 10 seconds, more preferably 1 to 5 seconds, even more preferably 2 to 5 seconds, and even more preferably 3 to 5 seconds. More preferably, the time is 2 to 4 seconds. Within this range, the thin film growth rate is low, and the step coverage and It has the advantage of being economical and easy to use.

[0028] In this description, the feeding time of the growth inhibitor for thin film formation is: Based on a chamber volume of 15 to 20 L and a flow rate of 0.5 to 5 mg / s (seconds), Specifically, the chamber volume (internal volume) is 18 L and the flow rate is 1 to 2 mg / s.

[0029] In a preferred embodiment of the thin film forming method, the thin film forming growth inhibitor is vaporized. and adsorbing the compound on a surface of a loaded substrate in an ALD chamber; and ii. iii) purging the interior of the ALD chamber with a purge gas; and The compound is vaporized and adsorbed on the surface of the loaded substrate in the ALD chamber. iv) second purging the interior of the ALD chamber with a purge gas. v) supplying a reaction gas into the ALD chamber; and vi) cooling the ALD chamber. The inside is purged with purge gas for the third time. In this case, the thin film growth rate is appropriate. Even if the deposition temperature is high during thin film formation, process by-products are effectively removed. The resistivity of the thin film is reduced and the step coverage is greatly improved. It has the advantage of being higher.

[0030] The thin film growth inhibitor and thin film precursor compound are preferably VFC (Vapor Flow Composite). ctrol method, DLI (Direct Liquid Injection) method, or LDS (liquid delivery system) method More preferably, the ALD chamber is transferred to the ALD chamber in the LDS mode. is transferred inside.

[0031] The amount of the thin film growth inhibitor and the precursor compound introduced into the ALD chamber ( The ratio of (mg / cycle) is preferably 1:1.5 to 1:20, more preferably is 1:2 to 1:15, more preferably 1:2 to 1:12, The ratio of layers is preferably 1:2.5 to 1:10, and the thin film growth per cycle is within this range. The reduction rate of GPC (growth (Å) per cycle) is high, and the reduction effect of process by-products is large. stomach.

[0032] 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 compound having a metal film precursor or a compound having a metal oxide film precursor. a metal nitride precursor compound or a silicon nitride precursor compound, the metal being preferred. Or tungsten, cobalt, chromium, aluminum, hafnium, vanadium, niobium Niobium, germanium, lanthanum group elements, actinium group elements, gallium, tantalum Titanium, nickel, iridium, and molybdenum. The present invention includes one or more selected from the group consisting of:

[0033] The metal film precursor, the metal oxide film precursor, and the metal nitride film precursor are, for example, metal halide films. Lithides, metal alkoxides, alkyl metal compounds, metal amino compounds, metal carbonylation and substituted or unsubstituted cyclopentadienyl metal compounds. The number of types of the above-mentioned compounds may be one or more, but is not limited thereto.

[0034] As a specific example, the metal film precursor, the metal oxide film precursor, and the metal nitride film precursor are each Tetrachlorotitanium, tetrachloroge Rumanium (tetrachloro germanium), tin tetrachloride (te trachloro tin; tin tetrachloride), tris(isopropyl)ethyl meth Tris(isopropyl)ethylmethyl amidogermanium ino germanium, tetraethoxy germanium germanium, tetramethyl tin, tetra Tetraethyltin, bis(acetylacetonate)tin isacetylacetonate tin, trimethylaluminum (trimethylaluminum thyl aluminum), tetrakis(dimethylamino)germanium (tetrakis(dimethylamino)germanium akis(dimethylamino) germanium), bis(n-butyl aryl bis(n-butylamino) germanium, Tetrakis(ethylmethylam)tin tin), tetrakis(dimethylamino)tin thylamino) tin), Co2(CO)8(dicobalt octacar) bonyl), Cp2Co(biscyclopentadienyl cobalt) , Co(CO)3(NO)(cobalt tricarbonyl nitrosyl ), and CpCo(CO)2 (cabalt dicarbonyl cyclopentene The group consisting of, but not limited to, one or more selected from the group consisting of butyl ether, ... It is not something that can be achieved.

[0035] The silicon nitride film precursor is, for example, (NH2)Si(NHMe)3, (NH2) Si(NHEt)3, (NH2)Si(NH n Pr)3, (NH2)Si(NH i Pr)3, ( NH2)Si(NH n Bu)3, (NH2)Si(NH i Bu)3, (NH2)Si(NH t Bu )3, (NMe2)Si(NHMe)3, (NMe2)Si(NHEt)3, (NMe2)Si (NH n Pr)3, (NMe2)Si(NH i Pr)3, (NMe2)Si(NH n Bu)3, ( NMe2)Si(NH i Bu), (NMe2)Si(NH t Bu)3, (NEt2)Si(N HMe)3, (NEt2)Si(NHEt)3, (NEt2)Si(NH n Pr)3, (NEt 2)Si(NH i Pr)3, (NEt2)Si(NH n Bu), (NEt2)Si(NH i Bu )3, (NEt2)Si(NH t Bu)3, (N n Pr2)Si(NHMe)3, (N n Pr2) Si(NHEt)3, (N nPr2)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) Born t Bu)3、(N i Pr2)Si(NHMe)3、(N i Pr2)Si(NHEt)3 、(N i Pr2)Si(NH n Pr)3、(N i Pr2)Si(NH i Pr)3、(N i Pr2)S i(NH n Bu)3、(N i Pr2)Si(NH i Bu)3、(N i Pr2)Si(NH t Bu)3 、(N n Bu2)Si(NHMe)3、(N n Bu2)Si(NHEt)3、(N n Bu2)Si (NH n Pr)3、(N n Bu2)Si(NH i Pr)3、(N n Bu2)Si(NH n Bu)3、 (N n Bu2)Si(NH i Bu)3、(N n Bu2)Si(NH t Bu)3、(N i Bu2)Si (NHMe)3、(N i Bu2)Si(NHEt)3、(N i Bu2)Si(NH n Pr)3、( N i Bu2)Si(NH i Pr)3、(Ni Bu2)Si(NH n Bu)3、(N i Bu2)Si( NH i Bu)3、(N i Bu2)Si(NH t Bu)3、(N t Bu2)Si(NHMe)3、( N t Bu2)Si(NHEt)3、(N t Bu2)Si(NH n Pr)3、(N t Bu2)Si( NH i Pr)3、(N t Bu2)Si(NH n Bu)3、(N t Bu2)Si(NH i Bu)3、( N t Bu2)Si(NH t Bu)3、(NH2)2Si(NHMe)2、(NH2)2Si(NH Et)2、(NH2)2Si(NH n Pr)2、(NH2)2Si(NH i Pr)2、(NH2)2 Born n Bu)2、(NH2)2Si(NH i Bu)2、(NH2)2Si(NH t Bu)2、 (NMe2)2Si(NHMe)2、(NMe2)2Si(NHEt)2、(NMe2)2Si( NH n Pr)2、(NMe2)2Si(NH i Pr)2、(NMe2)2Si(NH n Bu)2、( NMe2)2Si(NH i Bu)2、(NMe2)2Si(NH t Bu)2、(NEt2)2Si( NHMe)2、(NEt2)2Si(NHEt)2、(NEt2)2Si(NH n Pr)2、(N Et2)2Si(NH i Pr)2、(NEt2)2Si(NHn Bu)2、(NEt2)2Si(N H i Bu)2、(NEt2)2Si(NH t Bu)2、(N n Pr2)2Si(NHMe)2、(N n Pr2)2Si(NHEt)2、(N n Pr2)2Si(NH n Pr)2、(N n Pr2)2Si( NH i Pr)2、(N n Pr2)2Si(NH n Bu)2、(N n Pr2)2Si(NH i Bu)2、 (N n Pr2)2Si(NH t Bu)2、(N i Pr2)2Si(NHMe)2、(N i Pr2)2S i(NHEt)2、(N i Pr2)2Si(NH n Pr)2、(N i Pr2)2Si(NH i Pr) 2、(N i Pr2)2Si(NH n Bu)2、(N i Pr2)2Si(NH i Bu)2、(N i Pr2 )2Si(NH t Bu)2、(N n Bu2)2Si(NHMe)2、(N n Bu2)2Si(NHE t)2、(N n Bu2)2Si(NH n Pr)2、(N n Bu2)2Si(NH i Pr)2、(N n B u2)2Si(NH n Bu)2、(N n Bu2)2Si(NH i Bu)2、(N n Bu2)2Si(N H t Bu)2、(N i Bu2)2Si(NHMe)2、(N i Bu2)2Si(NHEt)2、(N i Bu2)2Si(NH n Pr)2、(N i Bu2)2Si(NH i Pr)2、(N i Bu2)2Si (NH n Bu)2、(N i Bu2)2Si(NH i Bu)2、(N i Bu2)2Si(NH t Bu)2 、(N t Bu2)2Si(NHMe)2、(N t Bu2)2Si(NHEt)2、(N t Bu2)2 Born n Pr)2、(N t Bu2)2Si(NH i Pr)2、(N t Bu2)2Si(NH n B u)2、(N t Bu2)2Si(NH i Bu)2、(N t Bu2)2Si(NH t Bu)2、Si( HNCH2CH2NH)2、Si(MeNCH2CH2NMe)2、Si(EtNCH2CH2N Et)2、Si( n PrNCH2CH2N n Pr)2、Si( i PrNCH2CH2N i Pr)2、 Si( n BuNCH2CH2N n Bu)2、Si( i BuNCH2CH2N i Bu)2、Si( t B uNCH2CH2N t Bu)2、Si(HNCHCHNH)2、 Si(MeNCHCHNMe)2、Si(EtNCHCHNEt)2、Si( n PrNCH CHN n Pr)2、Si( i PrNCHCHN i Pr)2、Si( n BuNCHCHN n Bu)2 ,Be( i BuNCHCHN i Bu)2、Si( t BuNCHCHN t Group)2、(HNCHC HNH)Si(HNCH2CH2NH)、(MeNCHCHNMe)Si(MeNCH2C H2NMe)、(EtNCHCHNEt)Si(EtNCH2CH2NEt)、( n PrNC HCHN n Pr)If( n PrNCH2CH2N n Pr)、( i PrNCHCHN i Pr)Si ( i PrNCH2CH2N i Pr)、( n BuNCHCHN n This)Si( n BuNCH2CH2 N n Bu)、( i BuNCHCHN i This)Si( i BuNCH2CH2N i Bu)、( t BuN CHCHN t This)Si( t BuNCH2CH2N t Bu)、(NH t Bu)2Si(HNCH2 CH2NH)、(NH t Bu)2Si(MeNCH2CH2NMe)、(NH t Bu)2Si( EtNCH2CH2NEt)、(NH t Bu)2Si(n PrNCH2CH2N n Pr)、(NH t Bu)2Si( i PrNCH2CH2N i Pr)、(NH t Bu)2Si( n BuNCH2CH2 N n Bu)、(NH t Bu)2Si( i BuNCH2CH2N i Bu)、(NH t Bu)2Si( t BuNCH2CH2N t Bu)、(NH t Bu)2Si(HNCHCHNH)、(NH t Bu) 2Si(MeNCHCHNMe)、(NH t Bu)2Si(EtNCCHCNet)、(N H t Bu)2Si( n PrNCHCHN n Pr)、(NH t Bu)2Si( i PrNCHCHN i Pr)、(NH t Bu)2Si( n BuNCHCHN n Bu)、(NH t Bu)2Si( i Bu NCHCHN i Bu)、(NH t Bu)2Si( t BuNCHCHN t ( i PrNCH 2CH2N i Pr)Si(NHMe)2、( i PrNCH2CH2N i Pr)Si(NHEt)2 、( i PrNCH2CH2N i Pr)Si(NH n Pr)2、( iPrNCH2CH2N i Pr)S i(NH i Pr)2, ( i PrNCH2CH2N i Pr)Si(NH n Bu)2, ( i PrNCH2 CH2N i Pr)Si(NH i Bu)2, ( i PrNCH2CH2N i Pr)Si(NH t Bu)2 , ( i PrNCHCHN i Pr)Si(NHMe)2, ( i PrNCHCHN i Pr)Si( NHEt)2, ( i PrNCHCHN i Pr)Si(NH n Pr)2, ( i PrNCHCHN i Pr)Si(NH i Pr)2, ( i PrNCHCHN i Pr)Si(NH n Bu)2, ( i Pr NCHCHN i Pr)Si(NH i Bu)2 and ( i PrNCHCHN i Pr)Si(NH t B u) one or more selected from the group consisting of 2, but is not limited thereto.

[0036] 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.

[0037] A preferred example of the thin film precursor compound is titanium tetrahalide. can be.

[0038] The titanium tetrahalide can be used as a metal precursor for a thin film-forming composition. Examples of the titanium tetrahalide include TiF4, TiCl4, and TiBr4. and TiI4, for example, TiCl4 is preferable from the economical viewpoint, but is not limited thereto.

[0039] The titanium tetrahalide has excellent thermal stability and exists in a liquid state without being decomposed at room temperature. Its presence makes it useful as a precursor in ALD (atomic layer deposition) to deposit thin films. It can be used for.

[0040] For 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. be.

[0041] The non-polar solvent is preferably selected from the group consisting of alkanes and cycloalkanes. In this case, an organic solvent having low reactivity and solubility and easy water management is used. Even if the deposition temperature increases during thin film formation, the step coverage is excellent. The advantage of this is that the ge is improved.

[0042] In a more preferred embodiment, the non-polar solvent is a C1 to C10 alkane. e) or C3 to C10 cycloalkanes, preferably or a C3 to C10 cycloalkane, in which case It has the advantages of low reactivity and solubility, and easy moisture control.

[0043] In this description, C1, C3 etc. refer to carbon numbers.

[0044] The cycloalkane is preferably a C3 to C10 monocycloalkane, Among the above monocycloalkanes, cyclopentane is liquid at room temperature. Since it has the highest vapor pressure, it is preferable to use a vapor deposition process, but is not limited thereto. It is not.

[0045] The non-polar solvent has, for example, a solubility in water (25° C.) of 200 mg / L or less. Preferably, it is 50 to 200 mg / L, more preferably, it is 135 to 175 mg / L. Within this range, the reactivity with the thin film precursor compound is low and moisture control is easy. This has the advantage that

[0046] In this description, the solubility is measured according to the measurement method and standard commonly used in the technical field to which the present invention pertains. As an example, the saturated solution may be subjected to HPLC (high-performance liquid chromatography). It can be measured by the fluoromatography method.

[0047] 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 is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, and even more preferably The content is preferably 40 to 90% by weight, and most preferably 70 to 90% by weight.

[0048] If the content of the non-polar solvent exceeds the upper limit, it may cause impurities and lead to resistance. The amount of impurities in the thin film increases, and the organic solvent is added when the content is less than the lower limit. In this case, the effect of improving step coverage by adding a solvent and the effect of removing impurities such as chlorine (Cl) ions are considered. However, there is a drawback in that it has little effect in reducing noise.

[0049] The thin film formation method may, for example, have a thin film growth rate per cycle calculated by the following Equation 1: The decrease in the rate (Å / cycle) is -5% or less, preferably -10% or less, and more preferably or less than -20%, more preferably less than -30%, and even more preferably less than -40%. % or less, and most preferably -45% or less. Within this range, the step coverage and the uniformity of the film thickness are excellent. It has excellent performance.

[0050] [Number 1] Reduction in thin film growth rate per cycle (%) = [(Thin film growth rate per cycle when using a thin film growth inhibitor -Thin film growth rate per cycle when no growth inhibitor for thin film formation was used) / Thin film growth rate per cycle when no thin film growth inhibitor was used] x 100

[0051] The thin film forming method is SIMS (Secondary Ion Mass Spectrometry). The intensity of residual halogen in the thin film formed after 200 cycles ( c / s; counts / sec, the number of secondary ions detected per second, is preferably 10,000 or less; More preferably, it is 8,000 or less, even more preferably, it is 7,000 or less, and even more preferably Within this range, it is effective in preventing corrosion and deterioration. .

[0052] In this description, the purging is preferably performed at 1,000 to 10,000 sccm (St andard Cubic Centimeter per Minute;cc (cm 3 ) / min, 1 atm, 0°C), more preferably 2, 000 to 7,000 sccm, more preferably 2,500 to 6,000 sccm m, within this range, the thin film growth rate per cycle is reduced in a preferred range, and This has the effect of reducing by-products.

[0053] The ALD (atomic layer deposition) process is used to fabricate integrated circuits (ICs) that require high aspect ratios. This is extremely advantageous in the fabrication of self-limiting integrated circuits. Excellent conformality and uniformity due to the thin film growth mechanism The advantages include good uniformity and precise thickness control.

[0054] The thin film formation method is preferably 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 in the range of 350 to 600°C. The deposition temperature is preferably in the range of 400 to 550° C. More preferably, the deposition temperature is in the range of 400 to 500° C. It has the effect of growing a thin film with excellent film quality while embodying the characteristics of the ALD process.

[0055] The thin film formation method is carried out at a deposition pressure ranging from 0.1 to 10 Torr, for example. , preferably at deposition pressures in the range of 0.5 to 5 Torr, most preferably 1 to 3 Torr. The deposition pressure is in the range of rr, and within this range, a thin film of uniform thickness can be obtained.

[0056] In this description, deposition temperature and deposition pressure refer to the temperature and pressure formed in a deposition chamber. or by the temperature and pressure applied to the substrate in the deposition chamber. It can be done.

[0057] The thin film forming method preferably includes the steps of: and / or increasing the temperature in the chamber to a deposition temperature. and purging the chamber by injecting an inert gas into the chamber before the injecting step. .

[0058] In addition, the present invention provides a thin film manufacturing apparatus capable of implementing the thin film manufacturing method, which is an ALD method. a chamber, a first vaporizer for vaporizing a growth inhibitor for thin film formation, and a vaporized growth inhibitor for thin film formation. A first transfer means for transferring the agent into the ALD chamber, and a second vaporizer for vaporizing the Ti-based thin film precursor. and a second transport means for transporting the vaporized Ti-based thin film precursor into the ALD chamber. The manufacturing apparatus includes a vaporizer and a transport means that are commonly used in the technical field to which the present invention pertains. There are no particular limitations as long as the vaporizer and transfer means are compatible with the above.

[0059] As a specific example, the thin film formation method will be described below. First, a substrate on which a thin film can be formed is placed in a deposition chamber capable of atomic layer deposition. do.

[0060] The substrate includes a semiconductor substrate such as a silicon substrate or a silicon oxide substrate.

[0061] The substrate may further have a conductive or insulating layer formed thereon.

[0062] In order to deposit a thin film on a substrate placed in the deposition chamber, the above-mentioned thin film forming device is A growth inhibitor and a thin film precursor compound or a mixture thereof with a non-polar solvent are each provided.

[0063] After that, the prepared thin film formation inhibitor is put into the vaporizer, and then it is converted into a gas phase and vaporized. The thin film formation inhibitor is transferred to the chamber and adsorbed on the substrate, and the non-adsorbed thin film formation inhibitor is purged. ing).

[0064] Next, the prepared thin film precursor compound or a mixture of the compound and a non-polar solvent is put into the vaporizer. Then, it is converted into a gas phase and transferred to a deposition chamber where it is adsorbed onto a substrate, forming a non-adsorbed thin film. The composition is allowed to purge.

[0065] In this description, the thin film forming inhibitor and thin film precursor compounds are delivered to the deposition chamber. One example of the method is a mass flow controller (MFC). A method of transporting volatilized gas using the Vapor Flow Control (FC) method VFC, or Liquid Mass Flow Control Liquid Delivery Roller (LMFC) method is used to transport liquids. A laser very system (LDS) is used, and preferably the LDS method is used.

[0066] At this time, a carrier is used to move the thin film formation inhibitor and the thin film precursor compound onto the substrate. The rear gas or dilution gas is argon (Ar), nitrogen (N2), or helium (He). The present invention uses one or more mixed gases selected from, but not limited to, do not have.

[0067] In this description, as an example of a purge gas, an inert gas is used, preferably The above-mentioned carrier gas or diluent gas is used.

[0068] Next, a reaction gas is supplied. The reaction gas is a gas that is commonly 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 contains a reducing agent, a nitriding agent or an oxidizing agent. The reducing agent reacts with the thin film precursor compound adsorbed on the substrate to form a metal thin film, and the The nitriding agent forms a thin metal nitride film, and the oxidizing agent forms a thin metal oxide film. is formed.

[0069] Preferably, the reducing agent is ammonia gas (NH3) or hydrogen gas (H2), The nitriding agent is nitrogen gas (N2), and the oxidizing agent is selected from H2O, H2O2, O2, O3, and N2O. The compound is one or more selected from the group consisting of:

[0070] An inert gas is then used to purge any remaining unreacted reactant gas. This allows the removal of not only excess reaction gases but also the by-products that are produced. This can be done.

[0071] As described above, the step of adsorbing the thin film formation inhibitor on the substrate, the step of adsorbing the thin film formation inhibitor on the substrate, A step of purging the substrate, a step of adsorbing a thin film precursor compound onto the substrate, and a step of removing the non-adsorbed thin film forming composition. Purging the product, supplying a reaction gas, and purging the remaining reaction gas. is regarded as one unit cycle, and the unit cycle is repeated to form a thin film of a desired thickness. can be repeated.

[0072] The number of times the unit cycle is repeated is, for example, 100 to 1000 times, preferably is 100 to 500 times, more preferably 150 to 300 times, This has the effect of allowing the desired thin film characteristics to be suitably exhibited.

[0073] FIG. 1 is a process diagram for explaining a conventional ALD process, and FIG. 2 is an embodiment of the present invention. FIG. 1 is a process diagram for explaining an ALD process according to an embodiment. In the case of carrying out the above process, that is, the growth inhibitor for thin film formation (SP(surface p thin-film-synthesis inhibitor (TSI)) as thin-film precursor compounds (e.g., TiCl4) is first adsorbed on the substrate surface to protect it. In the case of non-reactive cation, the reactant gas (e.g., NH3) reacts with the cations to form Process by-products such as HCl remain on the thin film (e.g. TiN), causing corrosion and deterioration. However, as shown in FIG. 2, the growth suppressor for thin film formation according to the present invention The inhibitor (SP) is pre-adsorbed before the thin film precursor compound (e.g., TiCl4) is adsorbed. In order to protect the substrate surface (Surface Protection), a thin film ( During the formation of TiN, HCl and By removing these process by-products together with the growth inhibitor for thin film formation, corrosion of the substrate and This prevents degradation, and furthermore, by appropriately lowering the thin film growth rate per cycle. It also improves step coverage and film thickness uniformity.

[0074] The semiconductor substrate of the present invention is characterized by being manufactured by the thin film forming method described above. In such cases, it is necessary to appropriately reduce the thin film growth rate by suppressing side reactions and to remove process by-products in the thin film. By removing the coating, corrosion and deterioration are prevented, and step coverage is achieved. ge) and the thin film thickness uniformity is significantly improved.

[0075] The prepared thin film preferably has a thickness of 20 nm or less and a resistivity of less than 0.1. 400μΩ·cm, halogen content is 10,000ppm or less, and step coverage rate Within this range, the performance as a diffusion barrier film is excellent and corrosion of metal wiring materials is prevented. The effect of the present invention is to reduce food intake, but is not limited to this.

[0076] The thin film has a thickness of, for example, 5 to 20 nm, preferably 10 to 20 nm, more preferably More preferably, it is 15 to 18.5 nm, and even more preferably, it is 17 to 18.5 nm. Within this range, there is an effect of excellent thin film properties.

[0077] The thin film has a specific resistance of, for example, 0.1 to 400 μΩ·cm, preferably 50 or more. At most 400 μΩ·cm, more preferably 200 to 400 μΩ·cm, and even more preferably is 300 to 400 μΩ cm, more preferably 330 to 380 μΩ cm, The most preferable range is 340 to 370 μΩ·cm. Within this range, the thin film properties are excellent. This has the effect of:

[0078] 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 ppm, more preferably 8,200 ppm or less or 1,000 to 8,200 ppm pm, and within this range, the thin film properties are excellent and corrosion of the metal wiring material is reduced. This has the effect of:

[0079] The thin film has, for example, 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.

[0080] The produced thin film may be, for example, a TiN or TiO2 thin film.

[0081] In the following, preferred embodiments and drawings are presented to aid in understanding the present invention. The drawings are merely illustrative of the present invention, and various modifications and variations within the scope of the scope and technical concept of the present invention are within the scope of the present invention. It will be apparent to those skilled in the art that variations and modifications are possible, and such variations and modifications may be made without departing from the spirit and scope of the present invention. It is to be understood that these are within the scope of the appended claims.

[0082] [Example] <Examples 1 to 7> The growth inhibitors for thin film formation listed in Table 1 below and TiCl4 as a thin film precursor compound The growth inhibitor for thin film formation (SP) was placed in a canister. LMFC (Liquid Mass Flow Control Unit) at room temperature. er) was heated to 150°C at a flow rate of 0.05g / min (0.83mg / sec). The thin film growth inhibitor vaporized in the vaporizer was then heated for 3 seconds. The substrate was loaded into the deposition chamber. Argon gas was then pumped in for 3000 s. Argon purging was performed by supplying argon at 1000 mL / min for 6 seconds. The pressure inside the chamber was controlled and maintained at 1.3 Torr.

[0083] Next, the prepared TiCl4 was placed in a separate canister and heated at room temperature in LMFC (Liq Using a uid Mass Flow Controller, the flow rate was 0.05g / min. The mixture was fed to a separate vaporizer heated to 150° C. at a flow rate of 0.83 mg / sec. TiCl4 was vaporized into the gas phase and then introduced into the deposition chamber for 3 seconds. After this, argon The gas was supplied at 3000 sccm for 6 seconds to perform argon purging. During the above and subsequent treatments, the pressure in the reaction chamber was controlled and maintained at 1.3 Torr.

[0084] Next, ammonia was introduced as a reactive gas into the reaction chamber for 5 seconds, and then the reaction was continued for 10 seconds. The substrate on which the metal thin film was to be formed was heated to 460°C. This process was repeated 200 times to form a self-limiting atomic layer. A TiN thin film (a TiN layer) was formed.

[0085] [Table 1]

[0086] <Comparative Example 1> In the method of Example 1, no growth inhibitor for thin film formation was used, and as a result, no adsorption occurred. The same method as in Example 1 was used, except that the step of purging the growth inhibitor for thin film formation was omitted. A thin film of TIN was formed on the substrate.

[0087] <Comparative Examples 2 and 3> In the method of Example 1, instead of the growth inhibitor for thin film formation listed in Table 1 above, pentane ( Pentane or Cyclopentane A thin film of TIN was formed on a substrate in the same manner as in Example 1, except for the above.

[0088] [Experimental Example] 1) Evaluation of deposition As shown in Table 2 below, 2-chloro-2-methylbutane was used in the form of a thin film. Example 1, in which the growth inhibitor was used, was compared with Comparative Example 1, in which the inhibitor was not used. As a result, the deposition rate was 0.20 Å / cycle, which is 55. The remaining Examples 2 to 7 showed similar deposition rates to Example 1. It was confirmed that the deposition rate was the same as that of the growth inhibitor for thin film formation according to the present invention. Comparative Examples 2 and 3, in which pentane or cyclopentane was used instead, had the same results as Comparative Example 1. It was confirmed that the deposition rate was the same as the CVD deposition rate. 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.

[0089] [Table 2]

[0090] In addition, as shown in Table 3 below, the growth inhibitor for thin film formation, 2-chloro-2- The deposition rate decreased continuously according to the amount of methylbutane added. It was confirmed that the method of Example 1-1 was used to obtain the following results: The same procedure as in Example 1 was carried out, except for the amount of the growth inhibitor for thin film formation added.

[0091] [Table 3]

[0092] 2) Impurity reduction properties The impurity reduction characteristics of the TiN thin films deposited in Example 1 and Comparative Example 1, i.e. In order to compare the characteristics of by-product reduction in the process, SIMS analysis was performed and the results are as follows: The results are shown in Table 4.

[0093] [Table 4]

[0094] As shown in Table 4, Example 1 used the growth inhibitor for thin film formation according to the present invention. It was confirmed that the amount of the fluoride was reduced to one-third of that in Comparative Example 1, in which the fluoride was not used. It was possible to do so.

[0095] FIG. 3 shows the results of Example 7 (SP-TiCl4) and Comparative Example 1 (TiCl4) of the present invention. FIG. 1 is a graph showing the change in film thickness with increasing number of ALD cycles for Example 7. It was confirmed that the thickness of the thin film was significantly reduced.

[0096] FIG. 4 shows the deposition rates (Å / cy) of Examples 7-1 to 7-3 of the present invention and Comparative Example 1. cle) per ALD cycle. Change in film thickness with change in feeding amount of growth inhibitor (SP) 1 is a graph showing the change in the thickness of the thin film formed by the growth inhibitor according to the present invention as in Comparative Example 1. In the absence of the growth inhibitors for thin film formation according to the present invention, the thin film thickness was 74 Å. In the case of Examples 7-1, 7-2, and 7-3 in which 0.7 mg, 1 mg, and 2 mg were added, It was confirmed that the film thicknesses were significantly thinner, at 0.35 Å, 0.2 Å, and 0.1 Å, respectively. Here, Examples 7-1, 7-2, and 7-3 are the same as those of Example 7. The same procedure as in Example 7 was carried out, except for the amount of growth inhibitor used.

[0097] 3) Step coverage characteristics The step coverage of the TiN thin films deposited in Example 1 and Comparative Example 1 was measured using TEM. The results are shown in Table 5 and FIG.

[0098] [Table 5]

[0099] 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 in Comparative Example 1, in which this was not used. came.

[0100] In addition, referring to the TEM photograph in Figure 5 below, the deposition of Example 1 (SP-TiCl4) The thickness uniformity of the top and bottom of the TiN thin film was 100%. The conformality of the thin film is superior to that of the thin film TIN. We were able to confirm that:

[0101] <Additional Example 1> In Example 1, tris(dimethylamino)cyclohexane was used instead of TiCl4 as the film precursor. Pentadienylzirconium (Tris(dimethylamino)cyclopentadiene CpZr) is used as a growth inhibitor for thin film formation. The injection rate into the chamber was set at 12 mg / sec, and instead of ammonia, ammonium was used as the reaction gas. The substrate on which the metal thin film was formed was heated to 280 to 340 degrees Celsius. The film formation process was carried out in the same manner as in Example 1, except for the above. ) was formed.

[0102] <Additional Example 2> In the additional embodiment 1, the injection rate of the growth inhibitor for thin film formation into the chamber was set to 2.3 mg / s. The substrate on which the metal thin film is formed is placed in the ec for 1 to 7 seconds. The film formation process was carried out in the same manner as in Additional Example 1, except that the temperature was increased to 10° C. A zirconia oxide film (ZrO2 thin film) was formed.

[0103] <Additional Comparative Example 1> Except that no growth inhibitor for thin film formation was used in Additional Example 1, The film formation process was carried out in the same manner as in Example 1 to form a zirconium oxide film (ZrO2 thin film).

[0104] Regarding the zirconium oxide films deposited in the additional examples 1 and 2 and the additional comparative example 1, The deposition rate, the reduction rate (%) and the thickness uniformity (%) were measured, and the results are shown in Table 6 and The results are shown in FIG. 6. Here, the thickness uniformity (%) was calculated by the following Equation 2.

[0105] [Number 2] Thickness uniformity (%) = [(MAX-MIN) / (2×AVERAGE)]×100%

[0106] The MAX, MIN, and AVERAGE are the maximum, minimum, and average thickness values, respectively. The thickness is measured at multiple points using an ellipsometer. The optical thickness was measured.

[0107] [Table 6]

[0108] As shown in Table 6, the film thickness was 1.0 μm and the film thickness was 1.0 μm. The zirconium oxide film (additional example 1) is a similar film to the zirconium oxide film (additional example 2). Compared to Comparative Example 1), the thin film thickness per ALD cycle with deposition temperature is 0.508 The decrease rate is very constant at 0.511 Å and ranges from 34.6 to 42.3%. The film thickness uniformity was reduced to 1.1 to 2.1%. It was confirmed that the fluctuation range was significantly small within the range.

[0109] FIG. 6 shows the results of the ALD cycles for Additional Example 2 and Additional Comparative Example 1. Change in feeding time (sec) of growth inhibitor (SP) for thin film formation 1 is a graph showing the change in deposition rate (Å / cycle) with the change in the amount of the additive. In the case of Comparative Example 1 where the thin film formation inhibitor according to the present invention was not used, The deposition rate was about 0.8 Å / cycle, and the thin film formation inhibitors according to the present invention were used. In the case of Additional Example 2 in which the deposition time was 1 second, 3 seconds, 5 seconds, and 7 seconds, the deposition rates were Approximately 0.56 Å / cycle, 0.52 Å / cycle, 0.51 Å / cycle, and 0 It was confirmed that the rate was significantly lower, at 0.50Å / cycle. P-SF-P-OF-P is a thin film growth inhibitor (SP) that is added, purge gas (P) is added, and the thin film is Precursor (SF), purge gas (P), reaction gas (OF), and purge gas (F) are fed in one This means that the cycle was performed, and X-2X-5-10-3-6 is the input time for each stage (S; sec ond, seconds), where X is an integer from 0 to 7. Note that X=0 represents Additional Comparative Example 1. In the specific embodiment, X is an integer from 1 to 7.

Claims

1. The following chemical formula 1 [Chemical formula 1] AnBmXo (wherein A is carbon, B is hydrogen or an alkyl having 1 to 3 carbon atoms, X is a halogen, n is an integer from 1 to 15, o is an integer of 1 or more, and m is 0 to 2n+1), which is at least one compound selected from the group consisting of 1,1-dichloroethane, 1,2-dichloroethane, dichloromethane, 2-chloropropane, 1-chloropropane, 1,2-dichloropropane, 1,3-dichloropropane, 2,2-dichloropropane, 1-chloropentane, 2-chloropentane, 3-chloropentane, chlorocyclopentane, n-butyl chloride, tert-butyl chloride, sec-butyl chloride, isobutyl chloride, 1,2-dichlorobenzene, 1,4-dichlorobenzene, trichloropropane, and 2-chloro-2-methylbutane, or 2-Methyl-1-pentane Characterized in that Growth inhibitor for thin film formation.

2. The following chemical formula 1 [Chemical formula 1] AnBmXo (wherein A is carbon, B is hydrogen or an alkyl having 1 to 3 carbon atoms, X is a halogen, n is an integer from 1 to 15, o is an integer of 1 or more, and m is 0 to 2n+1), which is at least one compound selected from the group consisting of 1,1-dichloroethane, 1,2-dichloroethane, dichloromethane, 2-chloropropane, 1-chloropropane, 1,2-dichloropropane, 1,3-dichloropropane, 2,2-dichloropropane, 1-chloropentane, 2-chloropentane, 3-chloropentane, chlorocyclopentane, n-butyl chloride, tert-butyl chloride, sec-butyl chloride, isobutyl chloride, 1,2-dichlorobenzene, 1,4-dichlorobenzene, trichloropropane, and 2-chloro-2-methylbutane, or 2-Methyl-1-pentane The method includes the step of introducing a growth inhibitor for thin film formation, which is a compound represented by the formula (I), into an ALD chamber and adsorbing the compound on a surface of a substrate loaded thereon, Thin film formation method.

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