Area-selective thin film formation using nucleation growth retardation

Abstract

According to an embodiment of the present application, a method for forming a film with area selectivity includes: a step of supplying a nucleation growth inhibitor into a chamber in which a substrate is placed, so that the nucleation growth inhibitor is adsorbed to a non-growth area of the substrate; a step of purging the inside of the chamber; a step of supplying a precursor into the chamber, so that the precursor is adsorbed to a growth area of the substrate; a step of purging the inside of the chamber; and a step of supplying a reaction material into the chamber, so that the reaction material reacts with the adsorbed precursor to form a film.

Description

Technical Field

[0001] This invention relates to a method for forming thin films, and more specifically, to a method for forming regionally selective thin films by utilizing nuclear growth inhibition. Background Technology

[0002] Patterning of semiconductor devices is achieved through the arrangement of various material layers and photolithography or etching processes. However, in the past few decades, the miniaturization of components has accelerated, and the required pattern size has shrunk to the nanometer (nm) level, increasing the cost and time required to form nanopatterns. Furthermore, there is a need to develop selective deposition processes that can produce self-aligned structures without requiring subsequent steps. Summary of the Invention

[0003] Technical issues

[0004] The purpose of this invention is to provide a thin film forming method that can be selected according to the region.

[0005] Other objects of the present invention will become clearer from the following detailed description.

[0006] Problem Solution

[0007] According to an embodiment of the present invention, a region-selective thin film formation method includes: a nucleation growth inhibitor supply step, supplying a nucleation growth inhibitor into a cavity containing a substrate, such that the nucleation growth inhibitor is adsorbed onto a non-growth region and a growth region of the substrate; a step of purifying the interior of the cavity; a precursor supply step, supplying a precursor into the cavity; a step of purifying the interior of the cavity; and a thin film formation step, supplying a reactant into the cavity, such that the reactant reacts with the adsorbed precursor to form a thin film, wherein the thickness of the thin film formed on the growth region of the substrate is greater than the thickness of the thin film formed on the non-growth region of the substrate, the non-growth region is a metal-containing film having one or more elements from Group I to Group 13 as a central element, the growth region includes Si or Ge as a central element, and the nucleation growth inhibitor can be represented by one of the following chemical formulas: 4, 6, and 8.

[0008] <Chemical Formula 4>

[0009]

[0010] In <Formula 4>, n is selected from integers from 1 to 8, m is selected from integers from 1 to 5, and R1 and R2 are selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms.

[0011] <Chemical Formula 6>

[0012]

[0013] In <Chemical Formula 6>, n is selected from integers from 1 to 8, m is selected from integers from 1 to 6, and R1 and R2 are selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms.

[0014] <Chemical Formula 8>

[0015]

[0016] In <Formula 8>, n is selected from integers from 0 to 8, R1 to R3 are selected from alkyl groups having 1 to 8 carbon atoms, and R4 is selected from hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 8 carbon atoms.

[0017] The metal-containing film may be a metal-containing film with one or more of the group IV elements including Zr, Hf and Ti as the center element.

[0018] The metal-containing film may be a metal-containing film with one or more of the group 5 elements including Nb and Ta as the center element.

[0019] The metal-containing film may be a metal-containing film with one or more of the group 6 elements including W as the central element.

[0020] The metal-containing film may be a metal-containing film with one or more of the Group 11 elements, including Cu, as the center element.

[0021] The metal-containing film may be a metal-containing film with one or more of the group 13 elements including Al as the central element.

[0022] The metal-containing film can be the metal itself.

[0023] The metal-containing film can be a metal oxide.

[0024] The metal-containing film may be a metal nitride.

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

[0026] The silicon-containing film may be selected from one or more of Si, SiO, SiN, SiCN, C-doped SiN, and SiON.

[0027] The growth region can be a germanium-containing film.

[0028] The precursor may be an organic compound with one or more of the Group 14 elements, including Si and Ge, as its central element.

[0029] The precursor can be represented by the following chemical formula 9:

[0030] <Chemical Formula 9>

[0031]

[0032] In <Chemical Formula 9>, M is one of the Group 14 elements, including Si and Ge, and R1 to R4 are each selected from hydrogen, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 1 to 10 carbon atoms, aromaticamino groups having 6 to 12 carbon atoms, aromaticalkylamino groups having 7 to 13 carbon atoms, cyclicamino groups having 3 to 10 carbon atoms, heterocyclicamino groups having 3 to 10 carbon atoms, heteroaromaticamino groups having 6 to 12 carbon atoms, alkylsilylamino groups having 2 to 10 carbon atoms, azide groups, and halogens.

[0033] The precursor can be represented by the following chemical formula 10:

[0034] <Chemical Formula 10>

[0035]

[0036] In <Chemical Formula 10>, M is one of the Group 14 elements including Si and Ge, and R1 to R6 are each selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 1 to 10 carbon atoms, aromaticamino groups having 6 to 12 carbon atoms, aromaticalkylamino groups having 7 to 13 carbon atoms, cyclicamino groups having 3 to 10 carbon atoms, heterocyclicamino groups having 3 to 10 carbon atoms, heteroaromaticamino groups having 6 to 12 carbon atoms, alkylsilylamino groups having 2 to 10 carbon atoms, azide groups, and halogens.

[0037] The precursor can be represented by the following chemical formula 11:

[0038] <Chemical Formula 11>

[0039]

[0040] In <Formula 11>, M is one of the Group 14 elements including Si and Ge. R1 to R5 are each selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, and R6 to R9 are each selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 1 to 10 carbon atoms, aromaticamino groups having 6 to 12 carbon atoms, aromaticalkylamino groups having 7 to 13 carbon atoms, cyclicamino groups having 3 to 10 carbon atoms, heterocyclicamino groups having 3 to 10 carbon atoms, heteroaromaticamino groups having 6 to 12 carbon atoms, alkylsilylamino groups having 2 to 10 carbon atoms, azide groups, and halogens.

[0041] The precursor can be represented by the following chemical formula 12:

[0042] <Chemical Formula 12>

[0043]

[0044] In <Formula 12>, M is one of the Group 14 elements including Si and Ge, R1 to R10 are each selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, and R11 to R14 are each selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 1 to 10 carbon atoms, aromaticamino groups having 6 to 12 carbon atoms, aromaticalkylamino groups having 7 to 13 carbon atoms, cyclicamino groups having 3 to 10 carbon atoms, heterocyclicamino groups having 3 to 10 carbon atoms, heteroaromaticamino groups having 6 to 12 carbon atoms, alkylsilylamino groups having 2 to 10 carbon atoms, azide groups, and halogens.

[0045] The precursor can be represented by the following chemical formula 13:

[0046] <Chemical Formula 13>

[0047]

[0048] In <Chemical Formula 13>, M is one of the Group 14 elements including Si and Ge, and R1 to R6 are each selected from hydrogen, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 1 to 10 carbon atoms, aromaticamino groups having 6 to 12 carbon atoms, aromaticalkylamino groups having 7 to 13 carbon atoms, cyclicamino groups having 3 to 10 carbon atoms, heterocyclicamino groups having 3 to 10 carbon atoms, heteroaromaticamino groups having 6 to 12 carbon atoms, alkylsilylamino groups having 2 to 10 carbon atoms, azide groups, and halogens.

[0049] The reactants can be one or more of O3, O2, H2O, H2O2, N2O, and NH3.

[0050] The thin film can be formed by chemical vapor deposition (metal-organic chemical vapor deposition, MOCVD) or atomic layer deposition (ALD).

[0051] Invention Effects

[0052] According to one embodiment of the present invention, when the nucleus growth inhibitor is adsorbed into the non-growth region, the subsequent supply of precursor is prevented from adsorbing into the non-growth region, thereby preventing the formation of a thin film in the non-growth region. Attached Figure Description

[0053] Figure 1 This is a flowchart schematically illustrating a thin film formation method based on an embodiment of the present invention.

[0054] Figure 2 It is a schematic illustration based on Figure 1 A chart of the supply cycle.

[0055] Figure 3 and Figure 4 This is a graph showing the thickness of the silicon oxide film in each cycle of a comparative example based on the present invention.

[0056] Figure 5 and Figure 6 This is a diagram showing the thickness of the silicon oxide film in each cycle according to an embodiment of the present invention. Detailed Implementation

[0057] Next, use Figures 1 to 6 Preferred embodiments of the invention will be described in more detail below. Embodiments of the invention may be modified in various ways, and the scope of the invention should not be construed as limited to the embodiments described below. These embodiments are provided to explain the invention in more detail to those skilled in the art. Therefore, the shapes of the elements shown in the figures may be exaggerated for emphasis.

[0058] Throughout this specification, when a part is described as including a certain element, unless otherwise specified, it does not mean that other elements are excluded, but rather that other elements may be further included.

[0059] The terms “approximately”, “substantially”, etc., used throughout this specification, when the manufacturing and material indications inherent in their meaning contain permissible errors, indicate a numerical value or close to that value. They are intended to prevent malicious infringers from improperly using the disclosure of accurate or absolute numerical values ​​mentioned to aid in understanding this application.

[0060] Throughout this specification, the term "alkyl" or "alkyl group" includes straight-chain 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, alkyl groups include methyl, ethyl, n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), tert-butyl (tBu), isobutyl (iBu), sec-butyl (sBu), n-pentyl, tert-pentyl, isopentyl, sec-pentyl, neopentyl, 3-pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecylyl, dodecyl, and their isomers, but are not limited thereto.

[0061] Throughout this specification, the term “membrane” may include, but is not limited to, “membrane” or “thin film”.

[0062] When the thin film is deposited using atomic layer deposition (ALD), the reactants do not deposit onto the substrate or underlying layer during the initial cycle, and deposition may require several cycles. This period is called the incubation time, which can vary depending on various conditions such as the characteristics of the reactants and the characteristics of the substrate or underlying layer to which the deposition is performed. This invention seeks to provide an improved method that overcomes the limitations of the prior art and utilizes the differences in incubation time and ALD deposition process to selectively deposit thin film materials.

[0063] Figure 1 This is a flowchart schematically illustrating a thin film formation method based on an embodiment of the present invention. Figure 2 It is a schematic illustration based on Figure 1 A chart of the supply cycle.

[0064] Place the substrate into the process chamber and adjust the following ALD process conditions. ALD process conditions may include the temperature of the substrate or process chamber, the pressure in the process chamber, and the flow rate.

[0065] First, the substrate is exposed to a nucleation growth inhibitor supplied to the cavity, the inhibitor being adsorbed onto the surface of the substrate. The substrate has non-growth regions and growth regions, and the nucleation growth inhibitor is adsorbed onto both regions to prevent the adsorption of metal precursors in subsequent processes.

[0066] The non-growth region can be a metal-containing film with one or more elements from Groups 1 to 13 as the center element. Specifically, the metal-containing film can be a metal-containing film with one or more elements from Group 4, including Zr, Hf, and Ti, as the center element. The metal-containing film can be a metal-containing film with one or more elements from Group 5, including Nb and Ta, as the center element. The metal-containing film can be a metal-containing film with one or more elements from Group 6, including W, as the center element. The metal-containing film can be a metal itself, a metal oxide, or a metal nitride.

[0067] The growth region may have one or more group 14 elements, including Si and Ge, as its central element. Specifically, the growth region may be a silicon-containing film. The silicon-containing film may be one or more selected from Si, SiO, SiN, SiCN, C-doped SiN, and SiON. Furthermore, the growth region may be a germanium-containing film.

[0068] The nuclear growth inhibitor can be represented by the following chemical formula 1.

[0069] <Chemical Formula 1>

[0070]

[0071] In <Chemical Formula 1>, n is 1 or 2, and R is selected from hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms.

[0072] The nuclear growth inhibitor can be represented by the following chemical formula 2.

[0073] <Chemical Formula 2>

[0074]

[0075] In <Chemical Formula 2>, n is chosen from integers from 1 to 5.

[0076] The nuclear growth inhibitor can be represented by the following chemical formula 3.

[0077] <Chemical Formula 3>

[0078]

[0079] In <Chemical Formula 3>, n is selected from integers from 0 to 8, R1 is selected from alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, and hydrogen atoms, and R2 is selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms.

[0080] The nuclear growth inhibitor can be represented by the following chemical formula 4.

[0081] <Chemical Formula 4>

[0082]

[0083] In <Chemical Formula 4>, n is selected from integers from 1 to 8, m is selected from integers from 1 to 5, and R1 and R2 are selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms.

[0084] The nuclear growth inhibitor can be represented by the following chemical formula 5.

[0085] <Chemical Formula 5>

[0086]

[0087] In <Formula 5>, n is selected from integers from 1 to 5, m is selected from integers from 0 to 8, R1 is selected from alkyl groups having 1 to 8 carbon atoms and hydrogen atoms, and R2 is selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms.

[0088] The nuclear growth inhibitor can be represented by the following chemical formula 6.

[0089] <Chemical Formula 6>

[0090]

[0091] In <Chemical Formula 6>, n is selected from integers from 1 to 8, m is selected from integers from 1 to 6, and R1 and R2 are selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms.

[0092] The nuclear growth inhibitor can be represented by the following chemical formula 7.

[0093] <Chemical Formula 7>

[0094]

[0095] In <Chemical Formula 7>, n is chosen from integers from 0 to 5, m is chosen from integers from 1 to 5, and R is chosen from alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, and aryl groups having 6 to 12 carbon atoms.

[0096] The nuclear growth inhibitor can be represented by the following chemical formula 8.

[0097] <Chemical Formula 8>

[0098]

[0099] In <Formula 8>, n is chosen from integers from 0 to 8, R1 to R3 are each alkyl groups having 1 to 8 carbon atoms, and R4 is chosen from hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 8 carbon atoms.

[0100] Subsequently, a purifying gas (for example, an inert gas such as Ar) is supplied to the cavity to remove or purify unadsorbed nucleation growth inhibitors or byproducts.

[0101] The substrate is then exposed to a precursor supplied to the cavity, causing the precursor to adhere to the surface of the substrate. The precursor may be an organic compound with one or more Group 14 elements, including Si and Ge, as its central element.

[0102] The precursor can be represented by the following chemical formula 9.

[0103] <Chemical Formula 9>

[0104]

[0105] In <Chemical Formula 9>, M is one of the Group 14 elements, including Si and Ge, and R1 to R4 are each selected from hydrogen, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 1 to 10 carbon atoms, aromaticamino groups having 6 to 12 carbon atoms, aromaticalkylamino groups having 7 to 13 carbon atoms, cyclicamino groups having 3 to 10 carbon atoms, heterocyclicamino groups having 3 to 10 carbon atoms, heteroaromaticamino groups having 6 to 12 carbon atoms, alkylsilylamino groups having 2 to 10 carbon atoms, azide groups, and halogens.

[0106] The precursor can be represented by the following chemical formula 10.

[0107] <Chemical Formula 10>

[0108]

[0109] In <Chemical Formula 10>, M is one of the Group 14 elements including Si and Ge, and R1 to R6 are each selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 1 to 10 carbon atoms, aromaticamino groups having 6 to 12 carbon atoms, aromaticalkylamino groups having 7 to 13 carbon atoms, cyclicamino groups having 3 to 10 carbon atoms, heterocyclicamino groups having 3 to 10 carbon atoms, heteroaromaticamino groups having 6 to 12 carbon atoms, alkylsilylamino groups having 2 to 10 carbon atoms, azide groups, and halogens.

[0110] The precursor can be represented by the following chemical formula 11.

[0111] <Chemical Formula 11>

[0112]

[0113] In <Formula 11>, M is one of the Group 14 elements including Si and Ge. R1 to R5 are each selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, and R6 to R9 are each selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 1 to 10 carbon atoms, aromaticamino groups having 6 to 12 carbon atoms, aromaticalkylamino groups having 7 to 13 carbon atoms, cyclicamino groups having 3 to 10 carbon atoms, heterocyclicamino groups having 3 to 10 carbon atoms, heteroaromaticamino groups having 6 to 12 carbon atoms, alkylsilylamino groups having 2 to 10 carbon atoms, azide groups, and halogens.

[0114] The precursor can be represented by the following chemical formula 12.

[0115] <Chemical Formula 12>

[0116]

[0117] In <Formula 12>, M is one of the Group 14 elements including Si and Ge, R1 to R10 are each selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, and R11 to R14 are each selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 1 to 10 carbon atoms, aromaticamino groups having 6 to 12 carbon atoms, aromaticalkylamino groups having 7 to 13 carbon atoms, cyclicamino groups having 3 to 10 carbon atoms, heterocyclicamino groups having 3 to 10 carbon atoms, heteroaromaticamino groups having 6 to 12 carbon atoms, alkylsilylamino groups having 2 to 10 carbon atoms, azide groups, and halogens.

[0118] The precursor can be represented by the following chemical formula 13.

[0119] <Chemical Formula 13>

[0120]

[0121] In <Chemical Formula 13>, M is one of the Group 14 elements including Si and Ge, and R1 to R6 are each selected from hydrogen, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 1 to 10 carbon atoms, aromaticamino groups having 6 to 12 carbon atoms, aromaticalkylamino groups having 7 to 13 carbon atoms, cyclicamino groups having 3 to 10 carbon atoms, heterocyclicamino groups having 3 to 10 carbon atoms, heteroaromaticamino groups having 6 to 12 carbon atoms, alkylsilylamino groups having 2 to 10 carbon atoms, azide groups, and halogens.

[0122] Subsequently, a purifying gas (for example, an inert gas such as Ar) is supplied to the cavity to remove or purify the unadsorbed precursors or byproducts.

[0123] Subsequently, the substrate is exposed to reactants supplied to the cavity to form a thin film on the substrate surface. The reactants react with the metal precursor to form the thin film, and the reactants can be one or more of O3, O2, H2O, H2O2, N2O, and NH3. The reactants are used to form oxides and nitrides, and can be replaced with substances other than those listed above, as needed.

[0124] Then, a purifying gas (for example, an inert gas such as Ar) is supplied to the cavity to remove or purify unreacted substances or byproducts.

[0125] Example

[0126] Using the aforementioned nucleus growth inhibitor, silicon oxide films are formed on the Si / SiN / SiO / TiN / HfO / NbO lower layers, respectively. The lower layer is either the substrate itself or formed via an ALD process. The silicon oxide films are formed via an ALD process at a temperature of 320°C, using ozone gas (O3) as the reactant.

[0127] The process of forming the silicon oxide film based on the ALD process is shown below, and is carried out in one cycle (see below). Figure 1 and Figure 2 ).

[0128] 1) Supply the nucleus growth inhibitor into the reaction chamber so that the nucleus growth inhibitor is adsorbed onto the substrate.

[0129] 2) Ar gas is supplied into the reaction chamber to remove unadsorbed nucleation growth inhibitors or byproducts.

[0130] 3) Using Ar as the carrier gas, the silicon precursor (diisopropylaminosilane (DIPAS)) is supplied to the reaction chamber, so that the silicon precursor is adsorbed onto the substrate.

[0131] 4) Ar gas is supplied into the reaction chamber to remove unadsorbed silicon precursors or byproducts.

[0132] 5) Ozone gas (O3) is supplied into the reaction chamber to form a silicon oxide film.

[0133] 6) Ar gas is supplied into the reaction chamber to remove unreacted substances or byproducts.

[0134] Comparative example

[0135] Without using the aforementioned nucleation growth inhibitor, silicon oxide films are formed on the Si / SiN / SiO / TiN / HfO / NbO lower layers, wherein the lower layer is the substrate itself or formed through an ALD process. The silicon oxide films are formed through an ALD process at a temperature of 320°C, and the reactant is ozone gas (O3).

[0136] The process of forming the silicon oxide film by the ALD process is shown below, and the following process is carried out as one cycle.

[0137] 1) Using Ar as the carrier gas, a silicon precursor (diisopropylaminosilane (DIPAS)) is supplied to the reaction chamber, so that the silicon precursor is adsorbed onto the substrate.

[0138] 2) Ar gas is supplied into the reaction chamber to remove unadsorbed silicon precursors or byproducts.

[0139] 3) Ozone gas (O3) is supplied into the reaction chamber to form a silicon oxide film.

[0140] 4) Ar gas is supplied into the reaction chamber to remove unreacted substances or byproducts.

[0141] Figure 3 and Figure 4 This is a graph showing the thickness of the silicon oxide film in each cycle of a comparative example based on the present invention. Figure 5 and Figure 6 This is a graph showing the thickness of the silicon oxide film in each cycle according to an embodiment of the present invention.

[0142] In the comparative example, the DIPAS used as the silicon-containing precursor does not have a selective incubation period based on the underlying layer (or substrate). Conversely, in the embodiment, depending on the underlying layer (or substrate), selective growth can occur within a specific period.

[0143] These results can be interpreted as follows: the nucleation growth inhibitor causes differences in the adsorption strength (degree) based on the underlying layer (or substrate), resulting in different incubation periods. That is, in the case of a underlying layer (or substrate) with strong adsorption strength (degree), the effect of hindering precursor adsorption is greater, making precursor adsorption and nucleation difficult, and resulting in low nucleation density. Conversely, in the case of a underlying layer (or substrate) with weak adsorption strength (degree), the effect of hindering precursor adsorption is smaller, making precursor adsorption and nucleation easier, and resulting in high nucleation density. Furthermore, the desired selectivity can be obtained due to other complex factors.

[0144] The present invention has been described in detail above with reference to embodiments, but other embodiments may still be included. Therefore, the technical ideas and scope described in the following claims are not limited to these embodiments.

[0145] Industrial applicability

[0146] This invention can be applied to various semiconductor manufacturing methods.

Claims

1. A method for forming a region-selective thin film, characterized in that, include: The nucleus growth inhibitor supply step involves supplying the nucleus growth inhibitor into a cavity containing a substrate, so that the nucleus growth inhibitor is adsorbed onto the non-growth area and the growth area of ​​the substrate. The steps of purifying the interior of the cavity; The precursor supply step involves supplying a precursor into the cavity; The steps of purifying the interior of the cavity; as well as In the thin film formation step, a reactant is supplied into the cavity, causing the reactant to react with the adsorbed precursor to form a thin film. The thickness of the thin film formed on the growth region of the substrate is greater than the thickness of the thin film formed on the non-growth region of the substrate. The non-growth region is a metal-containing film with one or more elements from Groups 1 to 13 as the central element, and the growth region includes Si or Ge as the central element. The nuclear growth inhibitor is represented by one of the following chemical formulas: 4, 6, or 8. <Chemical Formula 4> In <Chemical Formula 4>, n is selected from integers from 1 to 8, m is selected from integers from 1 to 5, and R1 and R2 are selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms. <Chemical Formula 6> In <Chemical Formula 6>, n is selected from integers from 1 to 8, m is selected from integers from 1 to 6, and R1 and R2 are selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms. <Chemical Formula 8> In <Formula 8>, n is selected from integers from 0 to 8, R1 to R3 are selected from alkyl groups having 1 to 8 carbon atoms, and R4 is selected from hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 8 carbon atoms.

2. The method for forming regionally selective thin films according to claim 1, characterized in that, The metal-containing film is a metal-containing film with one or more of the group IV elements including Zr, Hf and Ti as the center element.

3. The method for forming regionally selective thin films according to claim 1, characterized in that, The metal-containing film is a metal-containing film with one or more of the group 5 elements including Nb and Ta as the center element.

4. The method for forming regionally selective thin films according to claim 1, characterized in that, The metal-containing film is a metal-containing film with one or more of the group 6 elements including W as the central element.

5. The method for forming regionally selective thin films according to claim 1, characterized in that, The metal-containing film is a metal-containing film with one or more elements from Group 11, including Cu, as the center element.

6. The method for forming a regionally selective thin film according to claim 1, characterized in that, The metal-containing film is a metal-containing film with one or more elements from Group 13, including Al, as the central element.

7. The method for forming regionally selective thin films according to claim 1, characterized in that, The metal-containing film is the metal itself.

8. The method for forming regionally selective thin films according to claim 1, characterized in that, The metal-containing film is a metal oxide.

9. The method for forming a regionally selective thin film according to claim 1, characterized in that, The metal-containing film is a metal nitride.

10. The method for forming a regionally selective thin film according to claim 1, characterized in that, The growth region is a silicon-containing film.

11. The method for forming a regionally selective thin film according to claim 10, characterized in that, The silicon-containing film is selected from one or more of Si, SiO, SiN, SiCN, C-doped SiN, and SiON.

12. The method for forming a regionally selective thin film according to claim 1, characterized in that, The growth region is a germanium-containing film.

13. The method for forming a regionally selective thin film according to claim 1, characterized in that, The precursor is an organic compound with one or more of the Group 14 elements, including Si and Ge, as its central element.

14. The method for forming a regionally selective thin film according to claim 13, characterized in that, The precursor is represented by the following chemical formula 9: <Chemical Formula 9> In <Chemical Formula 9>, M is one of the Group 14 elements, including Si and Ge, and R1 to R4 are each selected from hydrogen, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 1 to 10 carbon atoms, aromaticamino groups having 6 to 12 carbon atoms, aromaticalkylamino groups having 7 to 13 carbon atoms, cyclicamino groups having 3 to 10 carbon atoms, heterocyclicamino groups having 3 to 10 carbon atoms, heteroaromaticamino groups having 6 to 12 carbon atoms, alkylsilylamino groups having 2 to 10 carbon atoms, azide groups, and halogens.

15. The method for forming a regionally selective thin film according to claim 13, characterized in that, The precursor is represented by the following chemical formula 10: <Chemical Formula 10> In <Chemical Formula 10>, M is one of the Group 14 elements including Si and Ge, and R1 to R6 are each selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 1 to 10 carbon atoms, aromaticamino groups having 6 to 12 carbon atoms, aromaticalkylamino groups having 7 to 13 carbon atoms, cyclicamino groups having 3 to 10 carbon atoms, heterocyclicamino groups having 3 to 10 carbon atoms, heteroaromaticamino groups having 6 to 12 carbon atoms, alkylsilylamino groups having 2 to 10 carbon atoms, azide groups, and halogens.

16. The method for forming a regionally selective thin film according to claim 13, characterized in that, The precursor is represented by the following chemical formula 11: <Chemical Formula 11> In <Formula 11>, M is one of the Group 14 elements including Si and Ge. R1 to R5 are each selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, and R6 to R9 are each selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 1 to 10 carbon atoms, aromaticamino groups having 6 to 12 carbon atoms, aromaticalkylamino groups having 7 to 13 carbon atoms, cyclicamino groups having 3 to 10 carbon atoms, heterocyclicamino groups having 3 to 10 carbon atoms, heteroaromaticamino groups having 6 to 12 carbon atoms, alkylsilylamino groups having 2 to 10 carbon atoms, azide groups, and halogens.

17. The method for forming a regionally selective thin film according to claim 13, characterized in that, The precursor is represented by the following chemical formula 12: <Chemical Formula 12> In <Formula 12>, M is one of the Group 14 elements including Si and Ge, R1 to R10 are each selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, and R11 to R14 are each selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 1 to 10 carbon atoms, aromaticamino groups having 6 to 12 carbon atoms, aromaticalkylamino groups having 7 to 13 carbon atoms, cyclicamino groups having 3 to 10 carbon atoms, heterocyclicamino groups having 3 to 10 carbon atoms, heteroaromaticamino groups having 6 to 12 carbon atoms, alkylsilylamino groups having 2 to 10 carbon atoms, azide groups, and halogens.

18. The method for forming a regionally selective thin film according to claim 13, characterized in that, The precursor is represented by the following chemical formula 13: <Chemical Formula 13> In <Chemical Formula 13>, M is one of the Group 14 elements including Si and Ge, and R1 to R6 are each selected from hydrogen, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 1 to 10 carbon atoms, aromaticamino groups having 6 to 12 carbon atoms, aromaticalkylamino groups having 7 to 13 carbon atoms, cyclicamino groups having 3 to 10 carbon atoms, heterocyclicamino groups having 3 to 10 carbon atoms, heteroaromaticamino groups having 6 to 12 carbon atoms, alkylsilylamino groups having 2 to 10 carbon atoms, azide groups, and halogens.

19. The method for forming a regionally selective thin film according to claim 1, characterized in that, The reactants are one or more of O3, O2, H2O, H2O2, N2O, and NH3.

20. The method for forming a regionally selective thin film according to claim 1, characterized in that, The thin film is formed by metal-organic chemical vapor deposition or atomic layer deposition.

Images