Organic small molecule inhibitors and methods for using them in thin film deposition

Abstract

This invention discloses organic small molecule inhibitors and methods for using them in thin film deposition, and belongs to the field of semiconductor processing technology. The inhibitors include urea-based compounds, amino acid-based compounds, and amidine-based compounds. The method of use involves placing a HAR substrate in an atomic layer deposition apparatus, introducing the organic small molecule inhibitor into the reaction chamber in pulse form using a stainless steel source bottle, introducing the precursor into the reaction chamber in pulse form using an inert gas as a carrier gas, introducing the precursor into the reaction chamber in pulse form using an oxygen source into the reaction chamber, generating an oxide thin film, introducing the inert gas into the reaction chamber, purging excess oxygen source and reaction byproducts, and repeating the above steps until a predetermined thickness is reached. Compared to previously reported inhibitor molecules, the inhibitors of this invention have two or more N and O atoms in their molecular structure, form multiple hydrogen bonds, have a better inhibitory effect, and significantly improve step coverage.

Description

TECHNICAL FIELD

[0001] The present invention falls within the technical field of semiconductor processing, and specifically relates to an organic small molecule inhibitor and a method of using the same in thin film deposition.

BACKGROUND ART

[0002] To continuously improve the minimization of device size and optimization of performance, the semiconductor industry has increasingly higher requirements for device storage density. Atomic Layer Deposition (ALD) is an excellent coating method, and has become a critical pre-process in the manufacturing process of semiconductor devices due to its significant advantages of isotropic growth and precise control of film thickness.

[0003] In high-aspect-ratio (HAR) 3D nanostructures, such as holes or trenches, ALD deposition often forms seams or voids during the top-to-bottom gap filling process, causing degradation of device performance, electrical conductivity or thermal conductivity performance and mechanical performance. To solve this problem, many researchers introduce inhibitors in the ALD deposition process to selectively inhibit the deposition at the top of the HAR substrate, and inhibit the deposition at the bottom less or not at all, so as to enhance the uniformity of top-to-bottom filling, improve the step coverage, and eliminate seams or gaps.

[0004] Patents CN104928654B and CN112400225A introduce plasma inhibitors (N2, Ar, He, H2, NH3, fluorides, amines, alcohols, etc.) to inactivate the surface and enhance the nucleation barrier of ALD film formation. When the plasma inhibitor interacts with the substrate, due to the geometric shadowing effect, the bottom receives much less plasma treatment than the top, which improves the step coverage of thin film growth. However, plasma causes damage to the substrate, and is also not suitable for use on HAR substrates with higher aspect ratios.

[0005] Patents CN113818009A and US20230227972A1 use an ALD precursor as an inhibitor, and the inhibitor in the inhibitory layer exhibits a density gradient that decreases from top to bottom on the HAR substrate. For example, a TiO2 thin film is deposited by an ALD process of tetrakis(dimethylamino)titanium (TDMAT) and H2O, and the step coverage is improved by introducing the inhibitor Cp*Ti(OMe)3, where Cp* is pentamethylcyclopentadienyl. This is because the inhibitor Cp*Ti(OMe)3 is strongly adsorbed to the substrate by removing -OMe, and because the steric hindrance of the Cp* ligand and its reactivity with H2O are weak, the Cp*Ti(OMe)x(1≦X≦2) on the substrate surface is not easily oxidized by H2O, making it difficult to form new Ti-O bonds and thus inhibiting the growth of the TiO2 thin film. [1] They investigated the inhibitory mechanism of the inhibitor Cp*Ti(OMe)3 in detail.

[0006] Patent US20220119939A1 proposes organic small molecule inhibitors, such as triethylamine (TEA), tetrahydrofuran (THF), and ethylene glycol dimethyl ether (DME). The inhibitor molecules mildly physically adsorb onto the HAR substrate, competing with the precursor molecule for the active site on the substrate surface. This inhibits excessive adsorption of the precursor to the substrate top and improves step coverage, although the effect needs to be improved.

[0007] Based on previous research, organic small molecule inhibitors are less expensive, more readily available, more environmentally friendly, and allow for easier adjustment and control of deposition process parameters compared to plasma gas inhibitors and ALD precursor system inhibitors. Therefore, searching for organic small molecule inhibitors with better efficacy is a worthwhile research endeavor. [Overview of the project]

[0008] The present invention aims to provide an organic small molecule inhibitor and a method for using it in thin film deposition, which solves the problem of the low effectiveness of conventional small molecule inhibitors for ALD deposition.

[0009] The object of the present invention can be achieved by the following technical solutions.

[0010] The present invention provides organic small molecule inhibitors comprising urea-based compounds, amino acid-based compounds, and amidine-based compounds.

[0011] Urea compounds have a structure represented by formula I. [ka] (Equation I)

[0012] In formula I, R1, R2, R3, and R4 are each independently selected from the group consisting of hydrogen, halogen, and any heteroatom-substituted group, and the heteroatom-substituted group includes any substituted aliphatic, any substituted cyclic aliphatic or heterocyclic aliphatic, and any substituted aromatic, and is typically a C1-C10 alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, alkyl halide, alkenyl halide, alkynyl halide, or heterocyclic halide group.

[0013] Preferably, the urea compound is one of urea, hydroxyethylurea, and semicarbazide.

[0014] Amino acid compounds have the structure represented by formula II. [ka] (Formula II)

[0015] In formula II, R1 and R2 are each independently selected from the group consisting of hydrogen, halogen, and any heteroatom-substituted group, and the heteroatom-substituted group includes any substituted aliphatic, any substituted cyclic aliphatic or heterocyclic aliphatic, and any substituted aromatic, and is typically a C1-C10 alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, alkyl halide, alkenyl halide, alkynyl halide, or heterocyclic halide group.

[0016] Preferably, the amino acid-based compound is one of glycine, alanine and isoleucine.

[0017] The amidine-based compound has a structure represented by Formula III.

Chemical Formula

[0018] In Formula III, R1, R2, R3, and R4 are each independently selected from the group consisting of hydrogen, halogen, and any group substituted with a heteroatom, and the any group substituted with a heteroatom includes any substituted aliphatic, any substituted cycloaliphatic or heterocycloaliphatic, and any substituted aromatic, and is usually a C1-C10 alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, halogenated alkyl, halogenated alkenyl, halogenated alkynyl, or halogenated heterocyclic group.

[0019] Preferably, the amidine-based compound is a formamidine-based compound, an acetamidine-based compound, or a propionamidine-based compound. For example, it is one of N,N'-diisopropyl-formamidine, N,N'-diisopropyl-acetamidine, N,N'-diisopropyl-propionamidine, N-hydroxyacetamidine, formamidine, acetamidine, and propionamidine.

[0020] Preferably, the halogen is one or more of F, Cl, Br, and I.

[0021] Preferably, the heteroatom is one or more of O, N, S, P, B, and Si.

[0022] Preferably, it is the use of the above-mentioned small organic molecule inhibitor in thin film deposition on HAR substrates with high aspect ratio.

[0023] The present invention further provides a method for using the aforementioned small organic molecule inhibitor in thin film deposition, and the method includes the following steps. In S1, the HAR substrate is placed into an atomic layer deposition apparatus, the heating temperature of the reaction chamber is set to 100-450°C, and vacuuming is performed to 0-30 Pa. In S2, the small organic molecule inhibitor is placed into a stainless steel source bottle, the source bottle is connected to the reaction chamber of the atomic layer deposition apparatus via a pipeline, the heating temperature of the source bottle is 30-100°C, the heating temperature of the pipeline is 50-150°C, an inert gas is used as a carrier gas, the small organic molecule inhibitor is introduced into the reaction chamber in a pulse mode, and the small organic molecule inhibitor forms hydrogen bonds with the surface active groups on the substrate. In S3, an inert gas is introduced into the reaction chamber to purge the excess small organic molecule inhibitor, and the purge time is set to 5-50 s. In S4, the precursor is placed into a stainless steel source bottle, the source bottle is connected to the reaction chamber via a pipeline, the heating temperature of the source bottle is 30-100°C, the heating temperature of the pipeline is 50-150°C, an inert gas is used as a carrier gas, the precursor is introduced into the reaction chamber in a pulse mode, and the precursor is chemically adsorbed with the surface active groups on the substrate. In S5, an inert gas is introduced into the reaction chamber to purge the excess precursor and reaction by-products, and the purge time is set to 5-50 s. In S6, an oxygen source is introduced into the reaction chamber in a pulse mode, the pulse time is 0.02-50 s, the flow rate is 20-200 sccm, and an oxide thin film is formed. In S7, an inert gas is introduced into the reaction chamber to purge the excess oxygen source and reaction by-products, and the purge time is set to 5-50 s. In S8, the steps S2 to S7 are repeated for X cycles until a predetermined thickness is reached, wherein X is an integer of 1 or more.

[0024] Preferably, in step S1, the aspect ratio of the HAR substrate is 30:1.

[0025] Preferably, in step S2, the pulse time is 0.02-5 s, and the flow rate of the carrier gas is 20-200 sccm.

[0026] Preferably, in step S4, the pulse time is 0.02-10 s and the carrier gas flow rate is 20-200 sccm.

[0027] Preferably, the precursor is a Si-based precursor or a metal-based precursor.

[0028] Preferably, the Si-based precursor is one or more of aminosilanes and halogenated silanes.

[0029] Preferably, the metallic precursor is one or more of the following: Ti metallic precursor, Zr metallic precursor, Hf metallic precursor, Nb metallic precursor, Co metallic precursor, Ni metallic precursor, V metallic precursor, Ta metallic precursor, lanthanum metallic precursor, Ru metallic precursor, Pt metallic precursor, Al metallic precursor, and Mg metallic precursor.

[0030] Preferably, the aminosilane is one or two of diisopropylaminesilane (DIPAS) and bis(tert-butylamino)silane (BTBAS).

[0031] Preferably, the Hf metal precursor is one or two of tris(dimethylamino)cyclopentadienylhafnium ([CpHf(NMe2)3]) and tetrakisethylmethylaminehafnium (TEMAHf).

[0032] Preferably, the Zr metal precursor is one or two of tris(dimethylamino)cyclopentadienylzirconium ([CpZr(NMe2)3]) and tetrakis(ethylmethylamine)zirconium (TEMAZr).

[0033] Preferably, the Ti metal precursor is trimethoxy(pentamethylcyclopentadienyl)titanium [Cp*Ti(OMe)3, abbreviated as Star-Ti].

[0034] Preferably, the Nb metal precursor is (tert-butylimino)bis(dimethylamino)(cyclopentadienyl)niobium([CpNb(N t It is one or two of the following: BuN)(NMe2)2) and tert-butyliminotris(diethylamino)niobium (TBTDEN).

[0035] Preferably, in step S6, the oxygen source is one or more of the following: O3, O2, H2O, H2O2, O2 plasma, etc.

[0036] Preferably, the inert gas is one of nitrogen (N2), argon (Ar), helium (He), and krypton (Kr).

[0037] Preferably, the HAR substrate includes, but is not limited to, inorganic materials such as silicon wafers, glass, and metals, or organic materials such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).

[0038] The beneficial effects of the present invention are as follows: The present invention provides three novel organic small molecule inhibitors having polyfunctional effects, which are urea-based compounds, amino acid-based compounds, and amidine-based compounds. Compared to previously reported inhibitor molecules, these three inhibitors have two or more N and O atoms in their molecular structure, form multiple hydrogen bonds, and exhibit better inhibitory effects. For example, urea contains ureido-N-CO-N-, amino acids contain carboxyl-COOH and amino-NH2, and amidine-based compounds contain two active N atoms. These active groups or atoms form multiple hydrogen bonds with the HAR substrate, occupying more active sites, more effectively inhibiting excessive adsorption of precursors at the top, thereby inhibiting the growth of the thin film at the top, while growth at the bottom is not inhibited or is weakly inhibited, significantly improving step coverage and eliminating the formation of seams or voids during the gap-filling process. [Modes for carrying out the invention]

[0039] The following describes the technical concepts in the embodiments of the present invention clearly and completely, in combination with the embodiments of the present invention. Of course, the embodiments described are only a selection of embodiments of the present invention, not all embodiments. All other embodiments obtained by those skilled in the art without creative work based on the embodiments of the present invention are all within the scope of protection of the present invention. Example 1

[0040] This embodiment provides a method for using organic small molecule inhibitors in thin film deposition, and includes the following steps. In S1, a silicon wafer (aspect ratio of 30:1) is placed in the atomic layer deposition apparatus, the reaction chamber is heated to 300°C, and the vacuum is reduced to 5 Pa. In S2, urea is placed in a stainless steel source bottle, which is connected to the reaction chamber of the atomic layer deposition apparatus via a conduit. The heating temperature of the source bottle is room temperature, and the heating temperature of the conduit is 150°C. Argon gas is used as the carrier gas, and urea is introduced into the reaction chamber in pulse form. The pulse duration is 0.08 s, and the carrier gas flow rate is 40 sccm. In step S3, argon gas is introduced into the reaction chamber to purge excess urea, and the purge time is set to 15 seconds. In S4, tris(dimethylamino)cyclopentadienylzirconium ([CpZr(NMe2)3]) is placed in a stainless steel source bottle, the source bottle is connected to the reaction chamber via a conduit, the heating temperature of the source bottle is set to 90°C, the heating temperature of the conduit is set to 150°C, argon gas is used as the carrier gas, tris(dimethylamino)cyclopentadienylzirconium is introduced into the reaction chamber in pulse form, the pulse time is set to 4 s, and the carrier gas flow rate is set to 40 sccm. In step S5, argon gas is introduced into the reaction chamber to purge excess tris(dimethylamino)cyclopentadienylzirconium and reaction byproducts, with a purging time of 25 seconds. In step S6, O3 is introduced into the reaction chamber in a pulsed manner, with a pulse duration of 0.1 s and a flow rate of 50 sccm, to produce an oxide thin film. In step S7, argon gas is introduced into the reaction chamber to purge excess O3 and reaction byproducts, with a purging time of 15 seconds. In S8, the processes S2-S7 are repeated 200 times. Example 2

[0041] This embodiment provides a method for using organic small molecule inhibitors in thin film deposition, and includes the following steps. In S1, a silicon wafer (aspect ratio of 30:1) is placed in the atomic layer deposition apparatus, the reaction chamber is heated to 300°C, and the vacuum is reduced to 5 Pa. In S2, glycine is placed in a stainless steel source bottle, which is connected to the reaction chamber of the atomic layer deposition apparatus via a conduit. The heating temperature of the source bottle is room temperature, and the heating temperature of the conduit is 150°C. Argon gas is used as the carrier gas, and glycine is introduced into the reaction chamber in pulse form. The pulse duration is 0.07 s, and the carrier gas flow rate is 40 sccm. In step S3, argon gas is introduced into the reaction chamber to purge excess glycine, and the purge time is set to 15 seconds. In step S4, tris(dimethylamino)cyclopentadienylzirconium ([CpZr(NMe2)3]) is placed in a stainless steel source bottle, which is connected to the reaction chamber via a conduit. The heating temperature of the source bottle is 90°C, and the heating temperature of the conduit is 150°C. Argon gas is used as the carrier gas, and tris(dimethylamino)cyclopentadienylzirconium is introduced into the reaction chamber in pulse form, with a pulse duration of 4 s and a carrier gas flow rate of 40 sccm. In step S5, argon gas is introduced into the reaction chamber to purge excess tris(dimethylamino)cyclopentadienylzirconium and reaction byproducts, with a purging time of 25 seconds. In step S6, O3 is introduced into the reaction chamber in a pulsed manner, with a pulse duration of 0.1 s and a flow rate of 50 sccm, to produce an oxide thin film. In step S7, argon gas is introduced into the reaction chamber to purge excess O3 and reaction byproducts, with a purging time of 15 seconds. In S8, the processes S2-S7 are repeated 200 times. Example 3

[0042] This embodiment provides a method for using organic small molecule inhibitors in thin film deposition, and includes the following steps. In S1, a silicon wafer (aspect ratio of 30:1) is placed in the atomic layer deposition apparatus, the reaction chamber is heated to 300°C, and the vacuum is reduced to 5 Pa. In S2, formamidine is placed in a stainless steel source bottle, the source bottle is connected to the reaction chamber of the atomic layer deposition apparatus via a conduit, the heating temperature of the source bottle is room temperature, the heating temperature of the conduit is 150°C, argon gas is used as the carrier gas, formamidine is introduced into the reaction chamber in pulse form, the pulse time is 0.05 s, and the carrier gas flow rate is 40 sccm. In step S3, helium gas is introduced into the reaction chamber to purge excess formamidine, and the purge time is set to 15 seconds. In step S4, tris(dimethylamino)cyclopentadienylzirconium ([CpZr(NMe2)3]) is placed in a stainless steel source bottle, which is connected to the reaction chamber via a conduit. The heating temperature of the source bottle is 90°C, and the heating temperature of the conduit is 150°C. Argon gas is used as the carrier gas, and tris(dimethylamino)cyclopentadienylzirconium is introduced into the reaction chamber in pulse form, with a pulse duration of 4 s and a carrier gas flow rate of 40 sccm. In step S5, argon gas is introduced into the reaction chamber to purge excess tris(dimethylamino)cyclopentadienylzirconium and reaction byproducts, with a purging time of 25 seconds. In step S6, O3 is introduced into the reaction chamber in a pulsed manner, with a pulse duration of 0.1 s and a flow rate of 50 sccm, to produce an oxide thin film. In step S7, argon gas is introduced into the reaction chamber to purge excess O3 and reaction byproducts, with a purging time of 15 seconds. In S8, the processes S2-S7 are repeated 200 times. Example 4

[0043] This embodiment provides a method for using the above-mentioned organic small molecule inhibitor in thin film deposition, and includes the following steps. In S1, a silicon wafer (aspect ratio of 30:1) is placed in the atomic layer deposition apparatus, the reaction chamber is heated to 350°C, and the vacuum is reduced to 5 Pa. In S2, hydroxyethyl urea is placed in a stainless steel source bottle, which is connected to the reaction chamber of the atomic layer deposition apparatus via a conduit. The heating temperature of the source bottle is room temperature, and the heating temperature of the conduit is 150°C. Argon gas is used as the carrier gas, and hydroxyethyl urea is introduced into the reaction chamber in pulse form, with a pulse duration of 0.3 s and a carrier gas flow rate of 40 sccm. In step S3, argon gas is introduced into the reaction chamber to purge excess hydroxyethylurea, and the purge time is set to 15 seconds. In step S4, tris(dimethylamino)cyclopentadienylhafnium ([CpHf(NMe2)3]) is placed in a stainless steel source bottle, which is connected to the reaction chamber via a conduit. The heating temperature of the source bottle is 80°C, and the heating temperature of the conduit is 150°C. Argon gas is used as the carrier gas, and tris(dimethylamino)cyclopentadienylhafnium is introduced into the reaction chamber in pulse form, with a pulse duration of 0.5 s and a carrier gas flow rate of 40 sccm. In step S5, argon gas is introduced into the reaction chamber to purge excess tris(dimethylamino)cyclopentadienylhafnium and reaction byproducts, with a purging time of 25 seconds. In S6, O3 is introduced into the reaction chamber in a pulsed manner, with a pulse duration of 5 s and a flow rate of 50 sccm. In step S7, argon gas is introduced into the reaction chamber to purge excess O3 and reaction byproducts, with a purging time of 15 seconds. In S8, the processes S2-S7 are repeated 200 times. Example 5

[0044] This embodiment provides a method for using an organic small molecule inhibitor in thin film deposition, and is the same as in Example 4, except that "hydroxyethylurea" in Example 4 is replaced with "alanine", the pulse time for alanine is 0.2 s, and the remaining raw materials and specific steps are the same as in Example 4. Example 6

[0045] This example provides a method for using an organic small molecule inhibitor in thin film deposition, and is different from Example 4 in that "hydroxyethylurea" is replaced with "N-hydroxyacetamidine," the pulse time for N-hydroxyacetamidine is 0.2 s, and the remaining raw materials and specific steps are the same as in Example 4. Example 7

[0046] This embodiment provides a method for using the above-mentioned organic small molecule inhibitor in thin film deposition, and includes the following steps. In S1, a silicon wafer (aspect ratio of 30:1) is placed in the atomic layer deposition apparatus, the reaction chamber is heated to 400°C, and the vacuum is reduced to 5 Pa. In S2, semicarbazide is placed in a stainless steel source bottle tube, the source bottle is connected to the reaction chamber of the atomic layer deposition apparatus via a conduit, the heating temperature of the source bottle is room temperature, the heating temperature of the conduit is 150°C, argon gas is used as the carrier gas, and semicarbazide is introduced into the reaction chamber in pulse form, with a pulse duration of 0.07 s and a carrier gas flow rate of 100 sccm. In step S3, argon gas is introduced into the reaction chamber to purge excess semicarbazide, with a purge time of 15 seconds. In S4, trimethoxy(pentamethylcyclopentadienyl)titanium ([Cp*Ti(OMe)3]) is abbreviated as Star-Ti and placed in a stainless steel source bottle. The source bottle is connected to the reaction chamber via a conduit. The heating temperature of the source bottle is 90°C, and the heating temperature of the conduit is 150°C. Argon gas is used as the carrier gas, and trimethoxy(pentamethylcyclopentadienyl)titanium is introduced into the reaction chamber in pulse form. The pulse duration is 0.15 s, and the carrier gas flow rate is 100 sccm. In step S5, an inert gas is introduced into the reaction chamber to purge excess trimethoxy(pentamethylcyclopentadienyl)titanium and reaction byproducts, with a purging time of 30 seconds. In step S6, O3 is introduced into the reaction chamber in a pulsed manner, with a pulse duration of 5 seconds and a flow rate of 50 sccm, to produce an oxide thin film. In step S7, argon gas is introduced into the reaction chamber to purge excess O3 and reaction byproducts, with a purging time of 20 seconds. In S8, the processes S2-S7 are repeated 200 times. Example 8

[0047] This embodiment provides a method for using an organic small molecule inhibitor in thin film deposition, and is the same as in Example 7, except that "semicarbazide" in Example 7 is replaced with "isoleucine", the heating temperature of the isoleucine source bottle is 30°C, the pulse time is 0.2 s, and the remaining raw materials and specific steps are the same as in Example 7. Example 9

[0048] This embodiment provides a method for using organic small molecule inhibitors in thin film deposition, and is the same as in Example 7, except that "semicarbazide" in Example 7 is replaced with "propionamidine", the pulse time for propionamidine is 0.3 s, and the remaining raw materials and specific steps are the same as in Example 7. Comparative Example 1

[0049] This comparative example provides a method for using organic small molecule inhibitors in thin film deposition. Compared to Example 1, steps S2 and S3 of Example 1 are removed, while the remaining raw materials and specific steps are the same as in Example 1. Comparative Example 2

[0050] This comparative example provides a method for using organic small molecule inhibitors in thin film deposition, and compared to Example 4, steps S2 and S3 of Example 4 are removed, while the remaining raw materials and specific steps are the same as in Example 4. Comparative Example 3

[0051] This comparative example provides a method for using organic small molecule inhibitors in thin film deposition, and compared to Example 7, steps S2 and S3 of Example 7 are removed, while the remaining raw materials and specific steps are the same as in Example 7. Comparative Example 4

[0052] This example provides a method for using an organic small molecule inhibitor in thin film deposition, and is the same as in Example 1, except that "urea" in Example 1 is replaced with "triethylamine", the pulse time for triethylamine is 0.2 s, and the remaining raw materials and specific steps are the same as in Example 1. Comparative Example 5

[0053] This example provides a method for using organic small molecule inhibitors in thin film deposition, and is different from Example 4 in that "hydroxyethyl urea" is replaced with "ethylene glycol dimethyl ether," the pulse time for ethylene glycol dimethyl ether is 0.2 s, and the remaining raw materials and specific steps are the same as in Example 4. Comparative Example 6

[0054] This embodiment provides a method for using an organic small molecule inhibitor in thin film deposition, and is the same as in Example 7, except that "semicarbazide" in Example 7 is replaced with "tetrahydrofuran," the pulse time for tetrahydrofuran is 0.02 s, and the remaining raw materials and specific steps are the same as in Example 7.

[0055] The deposited films obtained in Examples 1-9 and Comparative Examples 1-6 were detected, and the film thickness at the top and bottom of the HAR substrate was measured using a transmission electron microscope. Furthermore, the step coverage ratio was calculated. The model number of the apparatus was Talos F200X.

[0056] The method for calculating the step coverage ratio is shown below.

number

[0057] The test results are shown in Table 1.

[0058] [Table 1]

[0059] As can be seen from the records in Table 1, the step coverage rate and effectiveness were better with the small molecule inhibitors used in Examples 1-9 compared to Comparative Examples 1-3 which did not use inhibitors and Comparative Examples 4-6 which used small molecule inhibitors (triethylamine, ethylene glycol dimethyl ether, tetrahydrofuran). Compared to previously reported inhibitor molecules, the inhibitors of the present invention have two or more N and O atoms in their molecular structure, form multiple hydrogen bonds, have a better inhibitory effect, inhibit the growth of the thin film at the top, do not inhibit the growth at the bottom or have a weaker inhibitory effect, significantly improve the step coverage rate, and prove to eliminate the formation of seams or voids during the gap-filling process.

[0060] In this specification, relational terms such as "First" and "Second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply that such an actual relationship or order exists between these entities or operations. Furthermore, terms such as "includes," "has," or any other variation thereof are intended to cover non-exclusive inclusion, and a process, method, article, or device that includes a set of elements includes not only those elements but also other elements not explicitly listed, or elements specific to such a process, method, article, or device.

[0061] Although embodiments of the present invention have been described, those skilled in the art will understand that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is limited by the appended claims and equivalents.

Claims

1. A method for using organic small molecule inhibitors in thin film deposition, Step S1 involves placing the HAR substrate into an atomic layer deposition apparatus, setting the reaction chamber temperature to 100-450°C, and evacuating it to 0-30 Pa. Step S2 involves placing an organic small molecule inhibitor in a stainless steel source bottle and connecting it to a reaction chamber, with the source bottle heated to 30-100°C and the pipeline heated to 50-150°C, using an inert gas as a carrier gas, and introducing the organic small molecule inhibitor into the reaction chamber in a pulsed manner. Step S3 involves introducing an inert gas into the reaction chamber and setting the purging time to 5-50 s, Step S4 involves placing the precursor in a stainless steel source bottle, connecting the source bottle to the reaction chamber via a conduit, heating the source bottle to 30-100°C, heating the conduit to 50-150°C, using an inert gas as the carrier gas, and introducing the precursor into the reaction chamber in a pulsed manner. Step S5 involves introducing an inert gas into the reaction chamber and setting the purging time to 5-50 s, Step S6 involves introducing an oxygen source into the reaction chamber in pulse form, with a pulse duration of 0.02-50 s and a flow rate of 20-200 sccm. Step S7 involves introducing an inert gas into the reaction chamber and setting the purging time to 5-50 s, The process S2-S7 is repeated X times until a predetermined thickness is reached, and the process S8 includes a step where X is an integer of 1 or more. The aforementioned organic small molecule inhibitor is at least one selected from the group consisting of urea compounds, amino acid compounds, and amidine compounds. The urea-based compound has a structure represented by formula I, 【Chemistry 1】 (Equation I) In formula I, R1, R2, R3, and R4 are each independently selected from the group consisting of hydrogen, halogen, and any heteroatom-substituted group, and any heteroatom-substituted group includes any substituted aliphatic, any substituted cyclic aliphatic or heterocyclic aliphatic, and any substituted aromatic. The aforementioned amino acid compound has a structure represented by formula II, 【Chemistry 2】 (Formula II) In formula II, R1 and R2 are each independently selected from the group consisting of hydrogen, halogen, and any heteroatom-substituted group, and any heteroatom-substituted group includes any substituted aliphatic, any substituted cyclic aliphatic or heterocyclic aliphatic, and any substituted aromatic. The aforementioned amidine-based compound has a structure represented by formula III, 【Transformation 3】 (Formula III) A method for using an organic small molecule inhibitor in thin film deposition, characterized in that, in formula III, R1, R2, R3, and R4 are each independently selected from the group consisting of hydrogen, halogen, and any group substituted with a heteroatom, and the any group substituted with a heteroatom includes any substituted aliphatic, any substituted cyclic aliphatic or heterocyclic aliphatic, and any substituted aromatic.

2. The method for using an organic small molecule inhibitor in thin film deposition according to claim 1, characterized in that the precursor is a Si-based precursor or a metal-based precursor.

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