Region-selective thin film formation method using delayed nucleation growth

Abstract

According to one embodiment of the present invention, a method for forming a region-selective thin film includes a nucleus growth retarder supplying process for supplying a nucleus growth retarder into a chamber in which a substrate is placed and adsorbing it to a non-growth region of the substrate; a process for purging the inside of the chamber; a precursor supplying process for supplying a precursor into the chamber and adsorbing it to a growth region of the substrate; a process for purging the inside of the chamber; and a thin film formation process for supplying a reactant into the chamber and reacting with the adsorbed precursor to form a thin film.

Description

[Technical field]

[0001] The present invention relates to a method for forming a thin film, and more particularly to an area-selective method for forming a thin film using nuclear growth retardation. [Background technology]

[0002] Patterning of semiconductor devices is produced by deposition of various material layers and using lithography or etching processes. However, in the past decades, as the miniaturization of devices accelerated, the size of the required patterns decreased to the nanometer (nm) level, and the cost and time required for nanopatterning increased significantly. Furthermore, it is desirable to develop selective deposition processes that can obtain self-aligned structures without performing subsequent processes.

[0003] Detailed Description of the Invention technical challenges An object of the present invention is to provide a thin film formation method that allows selection according to the region. Other objects of the present invention will become more apparent from the following detailed description.

[0004] Problem solving means According to one embodiment of the present invention, the region selection target The thin film forming method includes supplying a nucleus growth retardant into a chamber in which a substrate is placed, and forming a non-growth region of the substrate. and growth areas a step of supplying a nucleation growth retardant that is adsorbed on the substrate; a step of purging the interior of the chamber; and a step of supplying a precursor to the interior of the chamber to remove the nucleation growth retardant from the substrate. The non-growth region and the The method includes a step of supplying a precursor that is adsorbed in a growth region; a step of purging the inside of the chamber; and a step of forming a thin film by supplying a reactant to the inside of the chamber and reacting with the adsorbed precursor. The non-growth region is a metal-containing film having at least one element selected from Groups 1 to 13 as a central element, and the growth region has at least one element selected from Group 14 elements including Si and Ge as a central element, and the non-growth region is formed of a material having a stronger adsorption strength of the nucleus growth retarder than the growth region. .

[0005] The nucleus growth retardant can be represented by the following <Chemical Formula 1>. [ka] In the above <Chemical Formula 1>, n=1, 2, R is selected from a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0006] The nucleus growth retardant can be represented by the following <Chemical Formula 2>. [ka] In the above <Chemical Formula 2>, n is independently selected from integers of 1 to 5.

[0007] The nucleus growth retardant can be represented by the following <Chemical Formula 3>. [ka] In the above <Chemical Formula 3>, n is independently selected from an integer of 0 to 8, R1 is independently selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a hydrogen atom; R2's are each independently selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0008] The nucleus growth retardant can be represented by the following <Chemical Formula 4>. [ka] In the above <Chemical Formula 4>, n is independently selected from an integer of 1 to 8, m is independently selected from an integer of 1 to 5; R1 and R2 are each independently selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0009] The nucleus growth retardant can be represented by the following <Chemical Formula 5>. [ka] In the above <Chemical Formula 5>, n is independently selected from an integer of 1 to 5, m is independently selected from an integer of 0 to 8; R1 is independently selected from an alkyl group having 1 to 8 carbon atoms or a hydrogen atom, R2's are each independently selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0010] The nucleus growth retardant can be represented by the following <Chemical Formula 6>. [ka] In the above <Chemical Formula 6>, n is independently selected from an integer of 1 to 8, m is independently selected from an integer of 1 to 6; R1 and R2 are each independently selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0011] The nucleus growth retardant can be represented by the following <Chemical Formula 7>. [ka] In the above <Chemical Formula 7>, n is independently selected from an integer of 0 to 5, m is independently selected from an integer of 1 to 5; R is independently selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0012] The nucleus growth retardant can be represented by the following <Chemical Formula 8>. [ka] In the above <Chemical Formula 8>, n is independently selected from an integer of 0 to 8, R1 to R3 each independently represent an alkyl group having 1 to 8 carbon atoms; R4 is selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms.

[0014] The metal-containing film may be a metal-containing film having at least one Group 4 element, including Zr, Hf, and Ti, as a central element.

[0015] The metal-containing film may be a metal-containing film having at least one of Group 5 elements including Nb and Ta as a central element.

[0016] The metal-containing film may be a metal-containing film having at least one Group 6 element, including W, as a central element.

[0017] The metal-containing film may be a metal-containing film having at least one Group 11 element, including Cu, as a central element.

[0018] The metal-containing film may be a metal-containing film having at least one Group 13 element, including Al, as a central element.

[0019] The metal-containing film can be the metal itself.

[0020] The metal-containing film can be a metal oxide.

[0021] The metal-containing film can be a metal nitride.

[0023] The growth region can be a silicon-containing film.

[0024] The silicon-containing film can be at least one selected from the group consisting of Si, SiO, SiN, SiCN, SiN doped with C atoms (C-doped SiN), and SiON.

[0025] The growth region can be a germanium-containing film.

[0026] The precursor may be an organic compound having at least one Group 14 element, including Si and Ge, as a central element.

[0027] The precursor can be represented by the following <Chemical Formula 9>. [ka] In the above <Chemical Formula 9>, M is one of the group 14 elements including Si and Ge. R1 to R4 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, a dialkylamine group having 1 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an aralkylamine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, a heteroarylamine group having 6 to 12 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, an azide group, or a halogen.

[0028] The precursor can be represented by the following <Chemical Formula 10>. [ka] In the above <Chemical Formula 10>, M is one of the group 14 elements including Si and Ge. R1 to R6 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, a dialkylamine group having 1 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an aralkylamine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, a heteroarylamine group having 6 to 12 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, an azide group, or a halogen.

[0029] The precursor can be represented by the following <Chemical Formula 11>. [ka] In the above <Chemical Formula 11>, M is one of the group 14 elements including Si and Ge. R1 to R5 are each independently selected from a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and R6 to R9 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, a dialkylamine group having 1 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an aralkylamine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, a heteroarylamine group having 6 to 12 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, an azide group, or a halogen.

[0030] The precursor can be represented by the following <Chemical Formula 12>. [ka] In the above <Chemical Formula 12>, M is one of the group 14 elements including Si and Ge. R1~R 10 are each independently selected from a hydrogen atom and an alkyl group having 1 to 10 carbon atoms; R 11 ~R 14 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, a dialkylamine group having 1 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an aralkylamine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, a heteroarylamine group having 6 to 12 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, an azide group, or a halogen.

[0031] The precursor can be represented by the following <Chemical Formula 13>. [ka] In the above <Chemical Formula 13>, M is one of the group 14 elements including Si and Ge. R1 to R6 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, a dialkylamine group having 1 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an aralkylamine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, a heteroarylamine group having 6 to 12 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, an azide group, or a halogen.

[0032] The reactant can be at least one of O3, O2, H2O, H2O2, N2O, and NH3.

[0033] The thin film can be formed by metalorganic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD).

[0034] Effect of the Invention According to one embodiment of the present invention, the nucleus growth retarder is adsorbed to the non-growth region to prevent a precursor that is subsequently supplied from being adsorbed to the non-growth region, thereby preventing a thin film from being formed in the non-growth region. [Brief description of the drawings]

[0035] [Figure 1] 1 is a flow chart illustrating a thin film forming method according to an embodiment of the present invention. [Diagram 2] 2 is a graph showing a schematic representation of a supply period according to FIG. 1; [Diagram 3] FIG. 11 is a graph showing thicknesses of silicon oxide films by cycles according to a comparative example of the present invention. [Figure 4] FIG. 11 is a graph showing thicknesses of silicon oxide films by cycles according to a comparative example of the present invention. [Diagram 5] 1 is a graph showing thicknesses of silicon oxide films for each cycle according to an embodiment of the present invention; [Figure 6] 1 is a graph showing thicknesses of silicon oxide films for each cycle according to an embodiment of the present invention; DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0036] Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the accompanying Figures 1 to 6. The embodiments of the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The present embodiments are provided to explain the present invention in more detail to those skilled in the art to which the present invention belongs. Therefore, the shape of each element shown in the drawings may be exaggerated to emphasize a clearer description.

[0037] Throughout this specification, when a part is said to "comprise" certain elements, this does not mean to exclude other elements, but means that it may further include other elements, unless otherwise specified.

[0038] As used throughout this specification, the terms "about," "substantially," and the like, when given the manufacturing and material tolerances inherent in the stated meaning, are used to mean a numerical value or approximation to that numerical value, and are used to aid in the understanding of the invention and to prevent unconscionable infringers from unfairly using disclosures in which precise or absolute numerical values ​​are recited.

[0039] Throughout this specification, the term "alkyl" or "alkyl group" includes linear or branched alkyl groups having 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 5 carbon atoms, 1 to 3 carbon atoms, 3 to 8 carbon atoms, or 3 to 5 carbon atoms. For example, the alkyl group includes methyl, ethyl, n-propyl, and propyl groups ( n Pr), isopropyl group ( i Pr), n-butyl group ( n Bu), tert-butyl group ( t Bu), iso-butyl group ( i Bu)), sec-butyl group ( sBu), n-pentyl group, tert-pentyl group, iso-pentyl group, sec-pentyl group, neopentyl group, 3-pentyl group, hexyl group, isohexyl group, heptyl group, 4,4-dimethylpentyl group, octyl group, 2,2,4-trimethylpentyl group, nonyl group, decyl group, undecyl group, dodecyl group, and isomers thereof.

[0040] Throughout this specification, the term "film" may include, but is not limited to, "membrane" or "thin film."

[0041] When depositing thin films by atomic layer deposition, reactants may not be deposited on the substrate or underlayer in the initial cycles, and several subsequent cycles may be required before deposition occurs. This period is called the incubation period, and the incubation period may vary depending on a variety of conditions, such as the characteristics of the reactants and the nature of the substrate or underlayer being deposited. The present invention aims to overcome the limitations of the prior art and provide an improved method for selectively depositing thin film materials by utilizing the difference between the ALD deposition process and the incubation period.

[0042] FIG. 1 is a flow chart that illustrates a thin film forming method according to one embodiment of the present invention, and FIG. 2 is a graph that illustrates a supply cycle according to FIG.

[0043] The substrate is loaded inside the process chamber, and the following ALD process conditions are adjusted: The ALD process conditions can include substrate or process chamber temperature, chamber pressure, and gas flow rates.

[0044] First, the substrate is exposed to a nucleus growth retardant supplied inside the chamber, and the nucleus growth retardant is adsorbed on the surface of the substrate. The substrate has a non-growth region and a growth region, and the nucleus growth retardant is adsorbed on the non-growth region and the growth region to prevent the precursor from being adsorbed in the subsequent process.

[0045] The non-growth region can be a metal-containing film having at least one of the elements of groups 1 to 13 as a central element. Specifically, the metal-containing film can be a metal-containing film having at least one of the elements of group 4 including Zr, Hf, and Ti as a central element, a metal-containing film having at least one of the elements of group 5 including Nb and Ta as a central element, a metal-containing film having at least one of the elements of group 6 including W as a central element, a metal-containing film having at least one of the elements of group 11 including Cu as a central element, or a metal-containing film having at least one of the elements of group 13 including Al as a central element, or can be a metal itself, a metal oxide, or a metal nitride.

[0046] The growth region may have one or more group 14 elements, including Si and Ge, as a central element. Specifically, the growth region may be a silicon-containing film, which may be one or more selected from Si, SiO, SiN, SiCN, SiN doped with C atoms (C-doped SiN), and SiON. The growth region may also be a germanium-containing film.

[0047] The nucleus growth retardant can be represented by the following <Chemical Formula 1>.

[0048] [ka] In the above <Chemical Formula 1>, n=1, 2, R is selected from a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0049] The nucleus growth retardant can be represented by the following <Chemical Formula 2>.

[0050] [ka] In the above <Chemical Formula 2>, n is independently selected from integers of 1 to 5.

[0051] The nucleus growth retardant can be represented by the following <Chemical Formula 3>.

[0052] [ka] In the above <Chemical Formula 3>, n is independently selected from an integer of 0 to 8, R1 is independently selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a hydrogen atom; R2's are each independently selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0053] The nucleus growth retardant can be represented by the following <Chemical Formula 4>.

[0054] [ka] In the above <Chemical Formula 4>, n is independently selected from an integer of 1 to 8, m is independently selected from an integer of 1 to 5; R1 and R2 are each independently selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0055] The nucleus growth retardant can be represented by the following <Chemical Formula 5>.

[0056] [ka] In the above <Chemical Formula 5>, n is independently selected from an integer of 1 to 5, m is independently selected from an integer of 0 to 8; R1 is independently selected from an alkyl group having 1 to 8 carbon atoms or a hydrogen atom, R2's are each independently selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0057] The nucleus growth retardant can be represented by the following <Chemical Formula 6>.

[0058] [ka] In the above <Chemical Formula 6>, n is independently selected from an integer of 1 to 8, m is independently selected from an integer of 1 to 6; R1 and R2 are each independently selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0059] The nucleus growth retardant can be represented by the following <Chemical Formula 7>.

[0060] [ka] In the above <Chemical Formula 7>, n is independently selected from an integer of 0 to 5, m is independently selected from an integer of 1 to 5; R is independently selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0061] The nucleus growth retardant can be represented by the following <Chemical Formula 8>.

[0062] [ka] In the above <Chemical Formula 8>, n is independently selected from an integer of 0 to 8, R1 to R3 each independently represent an alkyl group having 1 to 8 carbon atoms; R4 is selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms.

[0063] Thereafter, a purge gas (eg, an inert gas such as Ar) is supplied into the chamber to remove or purify any unadsorbed nucleus growth retardant or by-products.

[0064] The substrate is then exposed to a precursor supplied inside the chamber, and the precursor is adsorbed on the surface of the substrate. The precursor can be an organic compound having at least one of the group 14 elements, including Si and Ge, as a central element.

[0065] The precursor can be represented by the following <Chemical Formula 9>.

[0066] [ka] In the above <Chemical Formula 9>, M is one of the group 14 elements including Si and Ge. R1 to R4 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, a dialkylamine group having 1 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an aralkylamine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, a heteroarylamine group having 6 to 12 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, an azide group, or a halogen.

[0067] The precursor can be represented by the following <Chemical Formula 10>.

[0068] [ka] In the above <Chemical Formula 10>, M is one of the group 14 elements including Si and Ge. R1 to R6 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, a dialkylamine group having 1 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an aralkylamine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, a heteroarylamine group having 6 to 12 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, an azide group, or a halogen.

[0069] The precursor can be represented by the following <Chemical Formula 11>.

[0070] [ka] In the above <Chemical Formula 11>, M is one of the group 14 elements including Si and Ge. R1 to R5 are each independently selected from a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and R6 to R9 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, a dialkylamine group having 1 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an aralkylamine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, a heteroarylamine group having 6 to 12 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, an azide group, or a halogen.

[0071] The precursor can be represented by the following <Chemical Formula 12>.

[0072] [ka] In the above <Chemical Formula 12>, M is one of the group 14 elements including Si and Ge. R1~R 10 are each independently selected from a hydrogen atom and an alkyl group having 1 to 10 carbon atoms; R 11 ~R 14 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, a dialkylamine group having 1 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an aralkylamine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, a heteroarylamine group having 6 to 12 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, an azide group, or a halogen.

[0073] The precursor can be represented by the following <Chemical Formula 13>.

[0074] [ka] In the above <Chemical Formula 13>, M is one of the group 14 elements including Si and Ge. R1 to R6 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, a dialkylamine group having 1 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an aralkylamine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, a heteroarylamine group having 6 to 12 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, an azide group, or a halogen.

[0075] Thereafter, a purge gas (eg, an inert gas such as Ar) is supplied into the chamber to remove or purify any unadsorbed precursors or by-products.

[0076] The substrate is then exposed to a reactive material supplied inside the chamber to form a thin film on the surface of the substrate. The reactive material reacts with the precursor layer to form a thin film, and the reactive material can be at least one of O3, O2, H2O, H2O2, N2O, and NH3. The reactive material is for forming an oxide or nitride, and can be replaced with a material other than the exemplified materials as necessary.

[0077] Thereafter, a purge gas (eg, an inert gas such as Ar) is supplied into the chamber to remove or purify unreacted substances or by-products.

[0078] - Example Using the above-mentioned nucleus growth retardant, a silicon oxide film was formed on a lower layer of Si, SiN, SiO, TiN, HfO, or NbO, and the lower layer was formed on the substrate itself or through an ALD process. The silicon oxide film was formed by the ALD process, and the ALD process temperature was 320°C and O3 gas was used as a reactant.

[0079] The silicon oxide film formation process by the ALD process is as follows, and the following steps were performed as one cycle (see Figures 1 and 2). 1) A nucleus growth retardant is supplied into the reaction chamber and adsorbed onto the substrate. 2) Supply Ar gas into the reaction chamber to remove unadsorbed nucleus growth retardants or by-products. 3) Using Ar as a carrier gas, the silicon precursor DIPAS (Diisopropylamino Silane) is supplied to the reaction chamber, and the silicon precursor is adsorbed on the substrate. 4) Ar gas is supplied into the reaction chamber to remove any unadsorbed silicon precursor or by-products. 5) Supply O3 gas into the reaction chamber to form a silicon oxide film. 6) Ar gas is supplied into the reaction chamber to remove unreacted materials or by-products.

[0080] - Comparative Example Without using the above-mentioned nucleus growth retardant, a silicon oxide film was formed on a Si, SiN, SiO, TiN, HfO, or NbO underlayer, which was formed on the substrate itself or through an ALD process. The silicon oxide film was formed by an ALD process, and the ALD process temperature was 320°C and O3 gas was used as a reactant.

[0081] The silicon oxide film formation process by the ALD process is as follows, and the following steps were carried out as one cycle. 1) The silicon precursor DIPAS (Diisopropylamino Silane) is supplied to the reaction chamber using Ar as a carrier gas, and the silicon precursor is adsorbed on the substrate. 2) Ar gas is supplied into the reaction chamber to remove any unadsorbed silicon precursor or by-products. 3) Supply O3 gas into the reaction chamber to form a silicon oxide film. 4) Ar gas is supplied into the reaction chamber to remove unreacted materials or by-products.

[0082] 3 and 4 are diagrams showing the thickness of a silicon oxide film for each cycle in a comparative example of the present invention, and FIGS. 5 and 6 are diagrams showing the thickness of a silicon oxide film for each cycle in one embodiment of the present invention.

[0083] In the comparative example, DIPAS used as a Si-containing precursor has no incubation period without selectivity due to the underlayer (or substrate), whereas in the embodiment, the incubation period appears to be different depending on the underlayer (or substrate), and it can be seen that complete selective growth is possible in certain cycles.

[0084] This result is interpreted as a difference in the incubation period due to the difference in the adsorption strength (degree) of the nucleus growth retarder to the underlayer (or substrate). That is, in the case of a underlayer (or substrate) with a strong adsorption strength (degree) of the nucleus growth retarder, the effect of preventing precursor adsorption is large, precursor adsorption and nucleation are difficult, and the nucleation density is low, whereas in the case of a underlayer (or substrate) with a weak adsorption strength (degree) of the nucleus growth retarder, the effect of preventing precursor adsorption is small, precursor adsorption and nucleation are easy, and the nucleation density is high. As a result of other complex factors, the desired selectivity can be obtained. [Industrial Applicability]

[0085] The present invention is applicable to various types of semiconductor manufacturing methods.

Claims

1. a nucleus growth retardant supplying step of supplying a nucleus growth retardant into the chamber in which the substrate is placed and adsorbing the nucleus growth retardant on the non-growth region and the growth region of the substrate; purging the interior of the chamber; a precursor supply step of supplying a precursor into the chamber and adsorbing the precursor on the non-growth region and the growth region of the substrate; purging the interior of the chamber; and a thin film forming process in which a reactant is supplied into the chamber to react with the adsorbed precursor to form a thin film, the non-growth region is a metal-containing film having at least one element selected from Groups 1 to 13 as a central element, The growth region has at least one Group 14 element including Si and Ge as a central element, A region-selective thin film forming method, characterized in that the non-growth region is formed from a material having a stronger adsorption strength of the nucleus growth retardant than the growth region.

2. 2. The method of claim 1, wherein the nucleus growth retardant is represented by the following formula 1: In the above <Chemical Formula 1>, n=1, 2, R is selected from a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

3. 2. The method of claim 1, wherein the nucleus growth retardant is represented by the following formula 2: In the above <Chemical Formula 2>, n is independently selected from an integer of 1 to 5.

4. 2. The method of claim 1, wherein the nucleus growth retardant is represented by the following formula 3: In the above <Chemical Formula 3>, n is independently selected from an integer of 0 to 8, R 1 are each independently selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a hydrogen atom; R 2 are each independently selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

5. 2. The method of claim 1, wherein the nucleus growth retardant is represented by the following formula 4: In the above <Chemical Formula 4>, n is independently selected from an integer of 1 to 8, m is independently selected from an integer of 1 to 5; R 1 Or R 2 are each independently selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

6. 2. The method of claim 1, wherein the nucleus growth retardant is represented by the following formula: In the above <Chemical Formula 5>, n is independently selected from an integer of 1 to 5, m is independently selected from an integer of 0 to 8; R 1 are each independently selected from an alkyl group having 1 to 8 carbon atoms or a hydrogen atom; R 2 are each independently selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

7. 2. The method of claim 1, wherein the nucleus growth retardant is represented by the following formula 6: In the above <Chemical Formula 6>, n is independently selected from an integer of 1 to 8, m is independently selected from an integer of 1 to 6; R 1 Or R 2 are each independently selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

8. 2. The method of claim 1, wherein the nucleus growth retardant is represented by the following formula: In the above <Chemical Formula 7>, n is independently selected from an integer of 0 to 5, m is independently selected from an integer of 1 to 5; Each R is independently selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

9. 2. The method of claim 1, wherein the nucleus growth retardant is represented by the following formula 8: In the above <Chemical Formula 8>, n is independently selected from an integer of 0 to 8, R 1 ~R 3 are each independently an alkyl group having 1 to 8 carbon atoms, R 4 is selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms.

10. 2. The area selective thin film forming method according to claim 1, wherein said metal-containing film is a metal-containing film having at least one of Group 4 elements including Zr, Hf and Ti as a central element.

11. 2. The area selective thin film forming method according to claim 1, wherein said metal-containing film is a metal-containing film having at least one of Group 5 elements including Nb and Ta as a central element.

12. 2. The area selective thin film forming method according to claim 1, wherein said metal-containing film is a metal-containing film having at least one Group 6 element including W as a central element.

13. 2. The area selective thin film forming method according to claim 1, wherein said metal-containing film is a metal-containing film having at least one Group 11 element, including Cu, as a central element.

14. 2. The area selective thin film forming method according to claim 1, wherein said metal-containing film is a metal-containing film having at least one Group 13 element, including Al, as a central element.

15. 2. The method for selectively forming a thin film according to claim 1, wherein said metal-containing film is a metal itself.

16. 2. The method for selectively forming a thin film according to claim 1, wherein the metal-containing film is a metal oxide.

17. 2. The method for selectively forming a thin film according to claim 1, wherein the metal-containing film is a metal nitride.

18. 2. The method of claim 1, wherein the growth area is a silicon-containing film.

19. 20. The area selective thin film forming method according to claim 18, wherein the silicon-containing film is at least one selected from the group consisting of Si, SiO, SiN, SiCN, SiN doped with C atoms (C-doped SiN), and SiON.

20. 2. The method of claim 1, wherein the growth area is a germanium-containing film.

21. 2. The area selective thin film forming method according to claim 1, wherein said precursor is an organic compound having at least one Group 14 element, including Si and Ge, as a central element.

22. 22. The method of claim 21, wherein the precursor is represented by the following formula: In the above <Chemical Formula 9>, M is one of the group 14 elements including Si and Ge, R 1 ~R 4 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, a dialkylamine group having 1 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an aralkylamine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, a heteroarylamine group having 6 to 12 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, an azide group, or a halogen.

23. 22. The method of claim 21, wherein the precursor is represented by the following Formula 10: In the above <Chemical Formula 10>, M is one of the group 14 elements including Si and Ge, R 1 ~R 6 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, a dialkylamine group having 1 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an aralkylamine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, a heteroarylamine group having 6 to 12 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, an azide group, or a halogen.

24. 22. The method of claim 21, wherein the precursor is represented by the following formula: In the above <Chemical Formula 11>, M is one of the group 14 elements including Si and Ge, R 1 ~R 5 are each independently selected from a hydrogen atom and an alkyl group having 1 to 10 carbon atoms; R 6 ~R 9 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, a dialkylamine group having 1 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an aralkylamine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, a heteroarylamine group having 6 to 12 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, an azide group, or a halogen.

25. 22. The method of claim 21, wherein the precursor is represented by the following formula: In the above <Chemical Formula 12>, M is one of the group 14 elements including Si and Ge, R 1 ~R 10 are each independently selected from a hydrogen atom and an alkyl group having 1 to 10 carbon atoms; R 11 ~R 14 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, a dialkylamine group having 1 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an aralkylamine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, a heteroarylamine group having 6 to 12 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, an azide group, or a halogen.

26. 22. The method of claim 21, wherein the precursor is represented by the following formula: In the above <Chemical Formula 13>, M is one of the group 14 elements including Si and Ge, R 1 ~R 6 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylamine group having 1 to 10 carbon atoms, a dialkylamine group having 1 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an aralkylamine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, a heteroarylamine group having 6 to 12 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, an azide group, or a halogen.

27. The reactants are O 3 , O 2 , H 2 O,H 2 O 2 , N 2 O, N.H. 3 2. The method for selectively forming a thin film according to claim 1, wherein the method comprises at least one of the following steps.

28. 2. The method of claim 1, wherein the thin film is formed by metal-organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD).

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