An organic small molecule inhibitor and its application method in thin film deposition

Abstract

The invention discloses an organic small molecule inhibitor and an application method thereof in thin film deposition, belonging to the technical field of semiconductor processing. The inhibitor comprises urea compounds, amino acid compounds and amidine compounds. The application method is as follows: placing a HAR substrate into an atomic layer deposition device, placing the organic small molecule inhibitor in a stainless steel source bottle and introducing it into a reaction chamber in a pulsed form, placing a precursor in a stainless steel source bottle, using an inert gas as a carrier gas, and introducing the precursor into the reaction chamber in a pulsed form; introducing an oxygen source into the reaction chamber in a pulsed form to generate an oxide film; introducing an inert gas into the reaction chamber to purge excess oxygen source and reaction by-products, and repeating the above steps until a preset thickness is reached. Compared with reported inhibitor molecules, the inhibitor of the invention has two or more N and O atoms in its molecular structure, can form multiple hydrogen bonds, has a better inhibition effect, and significantly improves the step coverage.

Description

Technical Field

[0001] The invention belongs to the technical field of semiconductor processing, and in particular relates to an organic small molecule inhibitor and an application method thereof in thin film deposition. Background Art

[0002] In order to continuously improve the minimization of device size and optimization of performance, the semiconductor industry has put forward higher and higher requirements on the storage density of devices. Atomic layer deposition (ALD) is an excellent coating method. Due to its significant advantages of isotropic growth and precise control of film thickness, it has become a crucial front-end process in the semiconductor device manufacturing process.

[0003] In high aspect ratio (HAR) 3D nanostructures, such as holes or trenches, ALD deposition often forms seams or voids during the top-down gap filling process, resulting in reduced device performance, electrical or thermal conductivity, and mechanical properties. To address this problem, many researchers have introduced inhibitors during the ALD deposition process to selectively inhibit the deposition on the top of the HAR substrate, leaving less or no inhibition on the bottom, thereby enhancing the uniformity of top-down filling, improving step coverage, and eliminating seams or voids.

[0004] Patents CN104928654B and CN112400225A create a passivated surface and enhance the nucleation barrier of ALD film formation by introducing plasma inhibitors (N2, Ar, He, H2, NH3, fluorides, amines, alcohols, etc.). When the plasma inhibitor interacts with the substrate, due to the geometric shielding effect, the bottom receives much less plasma treatment than the top, thereby improving the step coverage of film growth. However, plasma can damage the substrate and is not suitable for use in HAR substrates with higher aspect ratios.

[0005] Patents CN113818009A and US20230227972A1 use ALD precursors as inhibitors, and the inhibitors in the inhibition layer show a density gradient that decreases from top to bottom in the HAR substrate. For example, the ALD process of tetrakis(dimethylamino)titanium (TDMAT) and H2O deposits TiO2 thin films, and the step coverage is improved by introducing the inhibitor Cp*T i(OMe)3, where Cp* is pentamethylcyclopentadienyl. This is because the inhibitor Cp*T i(OMe)3 is firmly adsorbed to the substrate by eliminating -OMe. Due to the steric hindrance of the Cp* ligand and its weak reaction ability with H2O, the Cp*T i(OMe)x (1≤X≤2) on the surface of the substrate is difficult to be oxidized by H2O, and it is difficult to form new TiO bonds, which inhibits the growth of TiO2 thin films. In addition, Chi Thang Nguyen [1]et al. explored the inhibitory mechanism of the inhibitor Cp*T i(OMe)3 in detail.

[0006] Patent US20220119939A1 proposes organic small molecule inhibitors. Taking triethylamine (TEA), tetrahydrofuran (THF), and ethylene glycol dimethyl ether (DME) as examples, the inhibitor molecules are gently physically adsorbed on the HAR substrate, competing with the precursor molecules for the active sites on the substrate surface, inhibiting the excessive adsorption of the precursor on the top of the substrate, thereby improving the step coverage, but the effect needs to be improved.

[0007] Based on existing research, compared with plasma gas inhibitors and ALD precursor inhibitors, organic small molecule inhibitors are cheap and easy to obtain, more environmentally friendly, and the deposition process parameters are easier to control. Therefore, finding better organic small molecule inhibitors is a meaningful research work. Summary of the invention

[0008] The purpose of the present invention is to provide an organic molecule small inhibitor and an application method thereof in thin film deposition, so as to solve the problem that the existing small molecule inhibitors for ALD deposition have poor effects.

[0009] The purpose of the present invention can be achieved through the following technical solutions:

[0010] The invention provides an organic small molecule inhibitor, comprising urea compounds, amino acid compounds and amidine compounds.

[0011] Urea compounds have the structure shown in Formula I:

[0012]

[0013] In Formula I, each of R1, R2, R3, and R4 is independently selected from the group consisting of:

[0014] Any group substituted by hydrogen, halogen, or heteroatom; any group substituted by heteroatom includes optionally substituted aliphatic, optionally substituted cycloaliphatic or heterocycloaliphatic, optionally substituted aromatic, typically C1-C10 alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, and halogenated heterocyclic group;

[0015] Preferably, the urea compound is one of urea, hydroxyethyl urea and semicarbazide.

[0016] The amino acid compound has the structure shown in Formula II:

[0017]

[0018] In Formula II, R1 and R2 are each independently selected from the group consisting of:

[0019] any group substituted by hydrogen, halogen, or heteroatom, wherein the heteroatom substituted group includes an optionally substituted aliphatic, an optionally substituted cycloaliphatic or heterocycloaliphatic, or an optionally substituted aromatic, typically C1-C10 alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, or halogenated heterocyclic group;

[0020] Preferably, the amino acid compound is one of glycine, alanine and isoleucine.

[0021] The amidine compound has the structure shown in formula III:

[0022]

[0023] In formula III, each of R1, R2, R3, and R4 is independently selected from the group consisting of:

[0024] any group substituted by hydrogen, halogen, or heteroatom, wherein the heteroatom substituted group includes an optionally substituted aliphatic, an optionally substituted cycloaliphatic or heterocycloaliphatic, or an optionally substituted aromatic, typically C1-C10 alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, or halogenated heterocyclic group;

[0025] Preferably, the amidine compound is a formamidine compound, an acetamidine compound, or a propionamidine compound, for example, one of N,N'-diisopropyl-formamidine, N,N'-diisopropyl-acetamidine, N,N'-diisopropyl-propionamidine, N-hydroxyacetamidine, formamidine, acetamidine, and propionamidine.

[0026] Preferably, the halogen is one or more of F, Cl, Br, and I.

[0027] Preferably, the heteroatom is one or more of O, N, S, P, B, and Si.

[0028] Preferably, the above-mentioned organic small molecule inhibitor is used in the deposition of HAR substrate thin films with a high aspect ratio.

[0029] The present invention also provides a method for applying the above-mentioned organic small molecule inhibitor in thin film deposition, comprising the following steps:

[0030] S1. Place the HAR substrate into the atomic layer deposition equipment, heat the reaction chamber to 100-450°C, and evacuate to 0-30Pa;

[0031] S2. The organic small molecule inhibitor is placed in a stainless steel source bottle, which is connected to the reaction chamber of the atomic layer deposition equipment through a pipeline. The heating temperature of the source bottle is 30-100° C., and the heating temperature of the pipeline is 50-150° C. An inert gas is used as a carrier gas, and the organic small molecule inhibitor is introduced into the reaction chamber in a pulsed form, so that the organic small molecule inhibitor forms H bonds with the surface active groups on the substrate;

[0032] S3, introducing inert gas into the reaction chamber to purge excess organic small molecule inhibitors for 5-50 seconds;

[0033] S4, the precursor is placed in a stainless steel source bottle, the source bottle is connected to the reaction chamber through a pipeline, the source bottle is heated at 30-100°C, the pipeline is heated at 50-150°C, an inert gas is used as a carrier gas, the precursor is introduced into the reaction chamber in a pulsed form, and the precursor will chemically adsorb with the surface active groups on the substrate;

[0034] S5, introducing an inert gas into the reaction chamber to purge excess precursor and reaction by-products for 5-50 seconds;

[0035] S6, introducing an oxygen source into the reaction chamber in a pulsed form, with a pulse time of 0.02-50 s and a flow rate of 20-200 sccm, to generate an oxide film;

[0036] S7, introducing an inert gas into the reaction chamber to purge excess oxygen source and reaction by-products for 5-50 seconds;

[0037] S8. Repeat steps S2-S7 for X cycles until a preset thickness is reached, where X is an integer greater than or equal to 1.

[0038] Preferably, in step S1, the aspect ratio of the HAR substrate is 30:1.

[0039] Preferably, in step S2, the pulse time is 0.02-5 s, and the carrier gas flow rate is 20-200 sccm.

[0040] Preferably, in step S4, the pulse time is 0.02-10 s, and the carrier gas flow rate is 20-200 sccm.

[0041] Preferably, the precursor is a Si-based precursor or a metal-based precursor.

[0042] Preferably, the Si-based precursor is one or more of aminosilane and halosilane.

[0043] Preferably, the metal-based precursor is one or more of a Ti metal-based precursor, a Zr metal-based precursor, a Hf metal-based precursor, a Nb metal-based precursor, a Co metal-based precursor, a Ni metal-based precursor, a V metal-based precursor, a Ta metal-based precursor, a lanthanide metal-based precursor, a Ru metal-based precursor, a Pt metal-based precursor, an Al metal-based precursor and a Mg metal-based precursor.

[0044] Preferably, the aminosilane is one or both of diisopropylaminesilane (D IPAS) and bis(tert-butylamino)silane (BTBAS).

[0045] Preferably, the Hf metal-based precursor is one or both of tris(dimethylamino)cyclopentadienylhafnium ([CpHf(NMe2)3]) and tetrakis(ethylmethylamino)hafnium (TEMAHf).

[0046] Preferably, the Zr metal-based precursor is one or both of tris(dimethylamino)cyclopentadienyl zirconium ([CpZr(NMe2)3]) and tetrakis(ethylmethylamino)zirconium (TEMAZr).

[0047] Preferably, the Ti metal-based precursor is trimethoxy(pentamethylcyclopentadienyl)titanium [Cp*T i(OMe) 3, referred to as Star-T i].

[0048] Preferably, the Nb metal-based precursor is (tert-butylimino)bis(dimethylamino)(cyclopentadienyl)niobium ([CpNb(N t One or both of BuN)(NMe2)2]) and tert-butyliminotris(diethylamino)niobium (TBTDEN).

[0049] Preferably, in step S6, the oxygen source is one or more of O3, O2, H2O, H2O2, and O2 plasma.

[0050] Preferably, the inert gas is one of nitrogen (N2), argon (Ar), helium (He) and krypton (He).

[0051] Preferably, the HAR substrate includes but is not limited to inorganic materials such as silicon wafer, glass, metal, etc. or organic materials such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.

[0052] Beneficial effects of the present invention:

[0053] The present invention proposes three new types of organic small molecule inhibitors with multi-functional group effects, namely urea compounds, amino acid compounds, and amidine compounds. Compared with the reported inhibitor molecules, the molecular structures of these three types of inhibitors have two or more N and O atoms, which will form multiple hydrogen bonds and have better inhibitory effects. For example, urea contains urea group -N-CO-N-, amino acids contain carboxyl group -COOH and amino group -NH2, and amidine compounds contain two active N atoms. These active groups or active atoms form multiple hydrogen bonds with the HAR substrate, occupy more active sites, and more effectively inhibit the excessive adsorption of the precursor at the top, thereby inhibiting the growth of the top film, while the bottom growth is not inhibited or the inhibition is very weak, significantly improving the step coverage and eliminating the formation of seams or gaps during gap filling. DETAILED DESCRIPTION

[0054] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0055] Example 1

[0056] This embodiment provides a method for applying an organic small molecule inhibitor in thin film deposition, comprising the following steps:

[0057] S1. Place the silicon wafer (with an aspect ratio of 30:1) into the atomic layer deposition equipment. The reaction chamber is heated to 300°C and evacuated to 5Pa.

[0058] S2, urea is placed in a stainless steel source bottle, the source bottle is connected to the reaction chamber of the atomic layer deposition equipment through a pipeline, the source bottle is heated at room temperature, the pipeline is heated at 150°C, argon is used as a carrier gas, urea is introduced into the reaction chamber in a pulsed form, the pulse time is 0.08s, and the carrier gas flow rate is 40sccm;

[0059] S3, introducing argon gas into the reaction chamber to purge excess urea for 15 seconds;

[0060] S4, tris(dimethylamino)cyclopentadienyl zirconium ([CpZr(NMe2)3]) is placed in a stainless steel source bottle, the source bottle is connected to the reaction chamber through a pipeline, the source bottle is heated at 90°C, the pipeline is heated at 150°C, argon is used as a carrier gas, tris(dimethylamino)cyclopentadienyl zirconium is introduced into the reaction chamber in a pulsed form, the pulse time is 4s, and the carrier gas flow rate is 40sccm;

[0061] S5, introducing argon gas into the reaction chamber to purge excess tris(dimethylamino)cyclopentadienyl zirconium and reaction by-products for 25 seconds;

[0062] S6, introducing O3 into the reaction chamber in pulse form, with a pulse time of 0.1 s and a flow rate of 50 sccm, to generate an oxide film;

[0063] S7, introducing argon gas into the reaction chamber to purge excess O3 and reaction by-products for 15 seconds;

[0064] S8. Repeat steps S2-S7 for 200 cycles.

[0065] Example 2

[0066] This embodiment provides a method for applying an organic small molecule inhibitor in thin film deposition, comprising the following steps:

[0067] S1. Place the silicon wafer (with an aspect ratio of 30:1) into the atomic layer deposition equipment. The reaction chamber is heated to 300°C and evacuated to 5Pa.

[0068] S2, glycine is placed in a stainless steel source bottle, the source bottle is connected to the reaction chamber of the atomic layer deposition equipment through a pipeline, the source bottle is heated at room temperature, the pipeline is heated at 150°C, argon is used as a carrier gas, glycine is introduced into the reaction chamber in a pulsed form, the pulse time is 0.07s, and the carrier gas flow rate is 40sccm;

[0069] S3, introducing argon gas into the reaction chamber to purge excess glycine for 15 seconds;

[0070] S4, tris(dimethylamino)cyclopentadienyl zirconium ([CpZr(NMe2)3]) was placed in a stainless steel source bottle, the source bottle was connected to the reaction chamber through a pipeline, the source bottle was heated at 90°C, the pipeline was heated at 150°C, argon was used as a carrier gas, tris(dimethylamino)cyclopentadienyl zirconium was introduced into the reaction chamber in a pulsed form, the pulse time was 4s, and the carrier gas flow rate was 40sccm;

[0071] S5, introducing argon gas into the reaction chamber to purge excess tris(dimethylamino)cyclopentadienyl zirconium and reaction by-products, the purge time is 25;

[0072] S6, introducing O3 into the reaction chamber in pulse form, with a pulse time of 0.1 s and a flow rate of 50 sccm, to generate an oxide film;

[0073] S7, introducing argon gas into the reaction chamber to purge excess O3 and reaction by-products for 15 seconds;

[0074] S8. Repeat steps S2-S7 for 200 cycles.

[0075] Example 3

[0076] This embodiment provides a method for applying an organic small molecule inhibitor in thin film deposition, comprising the following steps:

[0077] S1. Place the silicon wafer (with an aspect ratio of 30:1) into the atomic layer deposition equipment. The reaction chamber is heated to 300°C and evacuated to 5Pa.

[0078] S2, formamidine is placed in a stainless steel source bottle, the source bottle is connected to the reaction chamber of the atomic layer deposition equipment through a pipeline, the source bottle is heated to room temperature, the pipeline is heated to 150°C, argon is used as a carrier gas, formamidine is introduced into the reaction chamber in a pulsed form, the pulse time is 0.05s, and the carrier gas flow rate is 40sccm;

[0079] S3, introducing helium into the reaction chamber to purge excess formamidine for 15 seconds;

[0080] S4, tris(dimethylamino)cyclopentadienyl zirconium ([CpZr(NMe2)3]) was placed in a stainless steel source bottle, the source bottle was connected to the reaction chamber via a pipeline, the source bottle was heated at 90°C, the pipeline was heated at 150°C, argon was used as a carrier gas, tris(dimethylamino)cyclopentadienyl zirconium was introduced into the reaction chamber in a pulsed form, the pulse time was 4s, and the carrier gas flow rate was 40sccm;

[0081] S5, introducing argon gas into the reaction chamber to purge excess tris(dimethylamino)cyclopentadienyl zirconium and reaction by-products for 25 seconds;

[0082] S6, introducing O3 into the reaction chamber in pulse form, with a pulse time of 0.1 s and a flow rate of 50 sccm, to generate an oxide film;

[0083] S7, introducing argon gas into the reaction chamber to purge excess O3 and reaction by-products for 15 seconds;

[0084] S8. Repeat steps S2-S7 for 200 cycles.

[0085] Example 4

[0086] This embodiment provides a method for applying the above-mentioned organic small molecule inhibitor in thin film deposition, comprising the following steps:

[0087] S1. Place the silicon wafer (with an aspect ratio of 30:1) into the atomic layer deposition equipment. The reaction chamber is heated to 350°C and evacuated to 5Pa.

[0088] S2, hydroxyethyl urea is placed in a stainless steel source bottle, the source bottle is connected to the reaction chamber of the atomic layer deposition equipment through a pipeline, the source bottle is heated at room temperature, the pipeline is heated at 150°C, argon is used as a carrier gas, hydroxyethyl urea is introduced into the reaction chamber in a pulsed form, the pulse time is 0.3s, and the carrier gas flow rate is 40sccm;

[0089] S3, introducing argon gas into the reaction chamber to purge excess hydroxyethyl urea for 15 seconds;

[0090] S4, tris(dimethylamino)cyclopentadienyl hafnium ([CpHf(NMe2)3]) is placed in a stainless steel source bottle, the source bottle is connected to the reaction chamber through a pipeline, the source bottle is heated at 80°C, the pipeline is heated at 150°C, argon is used as a carrier gas, tris(dimethylamino)cyclopentadienyl hafnium is introduced into the reaction chamber in a pulsed form, the pulse time is 0.5s, and the carrier gas flow rate is 40sccm;

[0091] S5, introducing argon gas into the reaction chamber to purge excess tris(dimethylamino)cyclopentadienyl hafnium and reaction by-products for 25 seconds;

[0092] S6, introducing O3 into the reaction chamber in pulse form, with a pulse time of 5 s and a flow rate of 50 sccm;

[0093] S7, introducing argon gas into the reaction chamber to purge excess O3 and reaction by-products for 15 seconds;

[0094] S8. Repeat steps S2-S7 for 200 cycles.

[0095] Example 5

[0096] This embodiment provides an application method of an organic small molecule inhibitor in thin film deposition. Compared with Example 4, "hydroxyethyl urea" in Example 4 is replaced by "alanine", the alanine pulse time is 0.2s, and the remaining raw materials and specific steps are the same as Example 4.

[0097] Example 6

[0098] This embodiment provides an application method of an organic small molecule inhibitor in thin film deposition. Compared with Example 4, the "hydroxyethyl urea" in Example 4 is replaced by "N-hydroxyacetamidine", the pulse time of N-hydroxyacetamidine is 0.2s, and the remaining raw materials and specific steps are the same as Example 4.

[0099] Example 7

[0100] This embodiment provides a method for applying the above-mentioned organic small molecule inhibitor in thin film deposition, comprising the following steps:

[0101] S1. Place the silicon wafer (with an aspect ratio of 30:1) into the atomic layer deposition equipment. The reaction chamber is heated to 400°C and evacuated to 5Pa.

[0102] S2, placing semicarbazide in a stainless steel source bottle, connecting the source bottle to the reaction chamber of the atomic layer deposition equipment through a pipeline, heating the source bottle to room temperature, heating the pipeline to 150°C, using argon as a carrier gas, introducing semicarbazide into the reaction chamber in a pulsed form, the pulse time being 0.07s, and the carrier gas flow rate being 100sccm;

[0103] S3, introducing argon gas into the reaction chamber to purge excess semicarbazide for 15 seconds;

[0104] S4, trimethoxy (pentamethylcyclopentadienyl) titanium ([Cp*T i(OMe)3]), referred to as Star-T i, is placed in a stainless steel source bottle, the source bottle is connected to the reaction chamber through a pipeline, the source bottle is heated at 90°C, the pipeline is heated at 150°C, argon is used as a carrier gas, trimethoxy (pentamethylcyclopentadienyl) titanium is introduced into the reaction chamber in a pulsed form, the pulse time is 0.15s, and the carrier gas flow rate is 100sccm;

[0105] S5, introducing an inert gas into the reaction chamber to purge excess trimethoxy(pentamethylcyclopentadienyl)titanium and reaction by-products for 30 seconds;

[0106] S6, introducing O3 into the reaction chamber in pulse form, with a pulse time of 5 s and a flow rate of 50 sccm, to generate an oxide film;

[0107] S7, introducing argon gas into the reaction chamber to purge excess O3 and reaction by-products for 20 seconds;

[0108] S8. Repeat steps S2-S7 for 200 cycles.

[0109] Example 8

[0110] This embodiment provides an application method of an organic small molecule inhibitor in thin film deposition. Compared with Example 7, the "amino urea" in Example 7 is replaced by "isoleucine", the heating temperature of the source bottle of isoleucine is 30°C, the pulse time is 0.2s, and the remaining raw materials and specific steps are the same as Example 7.

[0111] Example 9

[0112] This embodiment provides an application method of an organic small molecule inhibitor in thin film deposition. Compared with Example 7, the "amino urea" in Example 7 is replaced by "propionamidine", the propionamidine pulse time is 0.3s, and the remaining raw materials and specific steps are the same as Example 7.

[0113] Comparative Example 1

[0114] This comparative example provides an application method of an organic small molecule inhibitor in thin film deposition. Compared with Example 1, step S2 and step S3 in Example 1 are removed, and the remaining raw materials and specific steps are the same as Example 1.

[0115] Comparative Example 2

[0116] This comparative example provides an application method of an organic small molecule inhibitor in thin film deposition. Compared with Example 4, step S2 and step S3 in Example 4 are removed, and the remaining raw materials and specific steps are the same as Example 4.

[0117] Comparative Example 3

[0118] This comparative example provides an application method of an organic small molecule inhibitor in thin film deposition. Compared with Example 7, step S2 and step S3 in Example 7 are removed, and the remaining raw materials and specific steps are the same as Example 7.

[0119] Comparative Example 4

[0120] This embodiment provides an application method of an organic small molecule inhibitor in thin film deposition. Compared with Example 1, "urea" in Example 1 is replaced by "triethylamine", the triethylamine pulse time is 0.2s, and the remaining raw materials and specific steps are the same as Example 1.

[0121] Comparative Example 5

[0122] This embodiment provides an application method of an organic small molecule inhibitor in thin film deposition. Compared with Example 4, the "hydroxyethyl urea" in Example 4 is replaced by "ethylene glycol dimethyl ether", the ethylene glycol dimethyl ether pulse time is 0.2s, and the remaining raw materials and specific steps are the same as Example 4.

[0123] Comparative Example 6

[0124] This embodiment provides an application method of an organic small molecule inhibitor in thin film deposition. Compared with Example 7, the "amino urea" in Example 7 is replaced by "tetrahydrofuran", the tetrahydrofuran pulse time is 0.02s, and the remaining raw materials and specific steps are the same as Example 7.

[0125] The deposited films obtained in Examples 1 to 9 and Comparative Examples 1 to 6 were tested, and the film thickness at the top and bottom of the HAR substrate was measured by a transmission electron microscope, and then the step coverage was calculated. The instrument model was Talos F200X;

[0126] The step coverage calculation method is as follows:

[0127]

[0128] The test results are shown in Table 1:

[0129] Table 1

[0130]

[0131]

[0132] It can be seen from the records in Table 1 that compared with Comparative Examples 1-3 which do not use inhibitors and Comparative Examples 4-6 which use small molecule inhibition (triethylamine, ethylene glycol dimethyl ether, tetrahydrofuran), the small molecule inhibition used in Examples 1-9 obtains higher step coverage and better effect, proving that compared with the reported inhibitor molecules, the inhibitor of the present invention has two or more N and O atoms in its molecular structure, which will form multiple hydrogen bonds and have better inhibition effect, inhibiting the growth of the top film, while the growth of the bottom is not inhibited or the inhibition is very weak, significantly improving the step coverage, and eliminating the formation of seams or voids during the gap filling process.

[0133] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0134] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for applying an organic small molecule inhibitor in thin film deposition, characterized in that: The following steps are involved: S1. Place the HAR substrate into the atomic layer deposition equipment, with the chamber temperature at 100-450°C and vacuum pumped to 0-30Pa; S2, placing the organic small molecule inhibitor in a stainless steel source bottle and connecting it to the reaction chamber, heating the source bottle at 30-100°C, heating the pipeline at 50-150°C, using inert gas as carrier gas, and passing the organic small molecule inhibitor into the reaction chamber in a pulsed form; S3, introducing inert gas into the reaction chamber for a purge time of 5-50s; S4, the precursor is placed in a stainless steel source bottle, the source bottle is connected to the reaction chamber through a pipeline, the source bottle is heated at 30-100°C, the pipeline is heated at 50-150°C, an inert gas is used as a carrier gas, and the precursor is introduced into the reaction chamber in a pulsed form; S5, introducing inert gas into the reaction chamber for a purge time of 5-50s; S6, introducing an oxygen source into the reaction chamber in a pulsed form, with a pulse time of 0.02-50 s and a flow rate of 20-200 sccm; S7, introducing inert gas into the reaction chamber for a purge time of 5-50s; S8, repeating steps S2-S7 for X cycles until a preset thickness is reached, where X is an integer greater than or equal to 1; The organic small molecule inhibitor includes one of a urea compound, an amino acid compound and an amidine compound; The urea compound is one of urea, hydroxyethyl urea and semicarbazide; The amino acid compound is one of glycine, alanine and isoleucine; The amidine compound is one of N,N'-diisopropyl-formamidine, N,N'-diisopropyl-acetamidine, N,N'-diisopropyl-propionamidine, N-hydroxyacetamidine and propionamidine.

2. The application method according to claim 1, characterized in that: The precursor is a Si-based precursor or a metal-based precursor.

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