Organic small molecule inhibitor and use method therefor in thin film deposition

Abstract

The present invention belongs to the technical field of semiconductor processing. Disclosed are an organic small molecule inhibitor and a use method therefor in thin film deposition, and. The inhibitor comprises a urea compound, an amino acid compound, and an amidine compound. The use method comprises: putting an HAR substrate into an atomic layer deposition device, loading the organic small molecule inhibitor into a stainless steel source bottle, introducing the organic small molecule inhibitor into a reaction cavity in a pulse form, installing a precursor in a stainless steel source bottle, taking an inert gas as a carrier gas, and introducing the precursor into the reaction cavity in a pulse form; introducing an oxygen source into the reaction cavity in a pulse form to generate an oxide thin film; and introducing inert gas into the reaction cavity, purging excessive oxygen source and reaction byproducts, and repeating the described steps until a preset thickness is reached. Compared with reported inhibitor molecules, the inhibitor of the present invention has two or more N and O atoms in the molecular structure, so that a plurality of hydrogen bonds can be formed, achieving a better inhibitory effect and significantly improving the step coverage rate.

Description

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

[0001] The present application belongs to the technical field of semiconductor processing, and particularly relates to an organic small molecule inhibitor and its application method in thin film deposition. BACKGROUND

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

[0003] In high aspect ratio (HAR) 3D nanostructures, such as holes or trenches, ALD deposition often forms seams or voids in the top-down gap filling process, resulting in reduced device performance, electrical or thermal conductivity performance, and mechanical performance. In order to solve this problem, many researchers introduce inhibitors in the ALD deposition process, which selectively inhibit the deposition on the top of the HAR substrate, and the bottom is less inhibited or not inhibited, thereby enhancing the uniformity of the top-down filling, improving the step coverage, and eliminating the seams or voids.

[0004] Patents CN104928654B and CN112400225A create a passivation surface by introducing plasma inhibitors (N2, Ar, He, H2, NH3, fluorides, amines, alcohols, etc.), which 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 compared to the top, thereby improving the step coverage of thin film growth. However, plasma can damage the substrate and is not suitable for application in HAR substrates with higher aspect ratios.

[0005] Patents CN113818009A and US20230227972A1 use ALD precursors as inhibitors, and the inhibitors in the inhibition layer exhibit a density gradient that decreases from the top to the bottom in the HAR substrate. For example, an ALD process of titanium tetrakis(dimethylamido) (TDMAT) and H2O deposits a TiO2 film, 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 firmly adsorbed to the substrate by eliminating -OMe, and the Cp*Ti(OMe)x (1≤X≤2) on the substrate surface is difficult to be oxidized by H2O due to the steric hindrance of the Cp* ligand and the weak reactivity with H2O, making it difficult to form new Ti-O bonds, thereby inhibiting the growth of the TiO2 film. In addition, Chi Thang Nguyen [1] et al. have studied the inhibition mechanism of the inhibitor Cp*Ti(OMe)3 in detail.

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

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

[0008] SUMMARY

[0009] The purpose of the present application is to provide an organic small-molecule inhibitor and its application method in thin film deposition, solving the problem of poor effect of existing ALD deposition small-molecule inhibitors.

[0010] The purpose of the present application can be achieved by the following technical solutions:

[0011] The present application provides an organic small-molecule inhibitor, which includes urea compounds, amino acid compounds, and amidine compounds.

[0012] The urea compound has a structure shown in Formula I:

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

[0014] hydrogen, halogen, any group substituted with a heteroatom, any group substituted with a heteroatom including optionally substituted aliphatic, optionally substituted cycloaliphatic or heterocycloaliphatic, optionally substituted aromatic, typically C1-C10 alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheterocyclyl;

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

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

[0017] In Formula II, each of R1, R2is independently selected from the group consisting of:

[0018] hydrogen, halogen, any group substituted with a heteroatom, any group substituted with a heteroatom including optionally substituted aliphatic, optionally substituted cycloaliphatic or heterocycloaliphatic, optionally substituted aromatic, typically C1-C10 alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheterocyclyl;

[0019] Preferably, the amino acid compound is one of glycine, alanine, and isoleucine.

[0020] The amidine compound has a structure shown in Formula III:

[0021] In Formula III, each of R1, R2, R3, R4is independently selected from the group consisting of:

[0022] hydrogen, halogen, any group substituted with a heteroatom, any group substituted with a heteroatom including optionally substituted aliphatic, optionally substituted cycloaliphatic or heterocycloaliphatic, optionally substituted aromatic, typically C1-C10 alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheterocyclyl;

[0023] Preferably, the amidine compound is one of formamidine, acetamidine, and propamidine. For example, one of N,N’-diisopropyl-formamidine, N,N’-diisopropyl-acetamidine, N,N’-diisopropyl-propamidine, N-hydroxyacetamidine, formamidine, acetamidine, and propamidine.

[0024] Preferably, the halogen is one or more of F, Cl, Br, I.

[0025] Preferably, the heteroatom is one or more of O, N, S, P, B, Si.

[0026] Preferably, the organic small molecule inhibitor is used in the deposition of a HAR substrate thin film with a high aspect ratio.

[0027] The application also provides a method for using the organic small molecule inhibitor in thin film deposition, comprising the following steps:

[0028] S1, placing the HAR substrate into an atomic layer deposition device, the reaction cavity heating temperature is 100-450℃, and the vacuum is extracted to 0-30Pa;

[0029] S2, the organic small molecule inhibitor is placed in a stainless steel source bottle, the source bottle is connected to the reaction cavity of the atomic layer deposition device through a pipeline, the source bottle heating temperature is 30-100℃, the pipeline heating temperature is 50-150℃, inert gas is used as the carrier gas, the organic small molecule inhibitor is introduced into the reaction cavity in the form of pulses, and the organic small molecule inhibitor and the surface active group on the substrate form a hydrogen bond;

[0030] S3, inert gas is introduced into the reaction cavity to purge excess organic small molecule inhibitor, and the purging time is 5-50s;

[0031] S4, the precursor is placed in a stainless steel source bottle, the source bottle is connected to the reaction cavity through a pipeline, the source bottle heating temperature is 30-100℃, the pipeline heating temperature is 50-150℃, inert gas is used as the carrier gas, the precursor is introduced into the reaction cavity in the form of pulses, and the precursor will be chemically adsorbed with the surface active group on the substrate;

[0032] S5, inert gas is introduced into the reaction cavity to purge excess precursor and reaction by-products, and the purging time is 5-50s;

[0033] S6, the oxygen source is introduced into the reaction cavity in the form of pulses, the pulse time is 0.02-50s, and the flow rate is 20-200sccm, to generate an oxide thin film;

[0034] S7, inert gas is introduced into the reaction cavity to purge excess oxygen source and reaction by-products, and the purging time is 5-50s;

[0035] S8, repeating steps S2-S7 for X cycles until the preset thickness is reached, wherein X is an integer greater than or equal to 1.

[0036] Preferably, the HAR substrate aspect ratio in step S1 is 30:1.

[0037] Preferably, the pulse time in step S2 is 0.02-5s, and the carrier gas flow rate is 20-200sccm.

[0038] Preferably, the pulse time in step S4 is 0.02-10s, and the carrier gas flow rate is 20-200sccm.

[0039] Preferably, the precursor is a Si-based precursor or a metal-based precursor.

[0040] Preferably, the Si-based precursor is one or more of an aminosilane and a halosilane.

[0041] 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.

[0042] Preferably, the aminosilane is one or both of diisopropylamine silane (DIPAS) and bis(tert-butylamino)silane (BTBAS).

[0043] Preferably, the Hf metal-based precursor is one or both of tris(dimethylamido)cyclopentadienyl hafnium ([CpHf(NMe2)3]) and hafnium tetra(ethylmethylamide) (TEMAHf).

[0044] Preferably, the Zr metal-based precursor is one or both of tris(dimethylamido)cyclopentadienyl zirconium ([CpZr(NMe2)3]) and zirconium tetra(ethylmethylamide) (TEMAZr).

[0045] Preferably, the Ti metal-based precursor is trimethoxy(pentamethylcyclopentadienyl)titanium [Cp*Ti(OMe)3, abbreviated as Star-Ti].

[0046] Preferably, the Nb metal-based precursor is one or both of (tert-butylimido)bis(dimethylamido)(cyclopentadienyl)niobium ([CpNb(N t BuN)(NMe2)2]) and tert-butylimido tris(diethylamido)niobium (TBTDEN).

[0047] Preferably, the oxygen source in step S6 is one or more of O3, O2, H2O, H2O2, and O2 plasma.

[0048] Preferably, the inert gas is one of nitrogen (N2), argon (Ar), helium (He), and krypton (He).

[0049] Preferably, the HAR substrate includes, but is not limited to, inorganic materials such as silicon wafers, glass, metals, and the like, or organic materials such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and the like.

[0050] Advantages of the present application:

[0051] The present application provides three new kinds of organic small molecule inhibitors with multi-functional effect, which are urea compounds, amino acid compounds and amidine compounds. Compared with the reported inhibitor molecules, the three kinds of inhibitors have two or more than two N and O atoms in the molecular structure, which can form multiple hydrogen bonds, and have better inhibition effect. For example, urea contains urea group-N-CO-N-, amino acid contains carboxyl group-COOH and amino group-NH2, and amidine compound contains two active N atoms. These active groups or active atoms form multiple hydrogen bonds with HAR substrate, occupy more active sites, more effectively inhibit the excessive adsorption of precursors on the top, thereby inhibiting the growth of the top film, the bottom growth is not inhibited or the inhibition effect is weak, and the step coverage is significantly improved, and the formation of joints or voids in the gap filling process is eliminated. DETAILED DESCRIPTION

[0052] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0053] Embodiment 1

[0054] The present embodiment provides a method for applying an organic small molecule inhibitor in thin film deposition, comprising the following steps:

[0055] S1, put the silicon wafer (aspect ratio of 30:1) into the atomic layer deposition equipment, the reaction cavity heating temperature is 300℃, and vacuum extraction is performed to 5Pa;

[0056] S2, put urea in a stainless steel source bottle, the source bottle is connected to the reaction cavity of the atomic layer deposition equipment through a pipeline, the source bottle heating temperature is room temperature, the pipeline heating temperature is 150℃, argon is used as the carrier gas, the urea is introduced into the reaction cavity in pulse form, the pulse time is 0.08s, and the carrier gas flow is 40sccm;

[0057] S3, introduce argon into the reaction cavity to blow off excess urea, and the blowing time is 15s;

[0058] S4, put tris(dimethylamino) cyclopentadienyl zirconium ([CpZr(NMe2)3]) in a stainless steel source bottle, the source bottle is connected to the reaction cavity through a pipeline, the source bottle heating temperature is 90℃, the pipeline heating temperature is 150℃, argon is used as the carrier gas, the tris(dimethylamino) cyclopentadienyl zirconium is introduced into the reaction cavity in pulse form, the pulse time is 4s, and the carrier gas flow is 40sccm;

[0059] S5, argon is introduced into the reaction cavity to purge excess tris(dimethylamine) cyclopentadienyl zirconium and reaction byproducts, and the purging time is 25 s;

[0060] S6, O3 is introduced into the reaction cavity in a pulse form, the pulse time is 0.1 s, the flow rate is 50 sccm, and an oxide film is generated;

[0061] S7, argon is introduced into the reaction cavity to purge excess O3 and reaction byproducts, and the purging time is 15 s;

[0062] S8, the steps S2-S7 are repeated for 200 cycles.

[0063] Example 2

[0064] The embodiment provides an application method of an organic small-molecule inhibitor in thin film deposition, and the method comprises the following steps:

[0065] S1, a silicon wafer (aspect ratio is 30:1) is placed into an atomic layer deposition device, the reaction cavity is heated to 300 DEG C, and vacuum is extracted to 5 Pa;

[0066] S2, glycine is placed in a stainless steel source bottle, the source bottle is connected to the reaction cavity of the atomic layer deposition device through a pipeline, the source bottle is heated to room temperature, the pipeline is heated to 150 DEG C, argon is used as a carrier gas, the glycine is introduced into the reaction cavity in a pulse form, the pulse time is 0.07 s, and the carrier gas flow rate is 40 sccm;

[0067] S3, argon is introduced into the reaction cavity to purge excess glycine, and the purging time is 15 s;

[0068] S4, tris(dimethylamine) cyclopentadienyl zirconium ([CpZr(NMe2)3]) is placed in a stainless steel source bottle, the source bottle is connected to the reaction cavity through a pipeline, the source bottle is heated to 90 DEG C, the pipeline is heated to 150 DEG C, argon is used as a carrier gas, the tris(dimethylamine) cyclopentadienyl zirconium is introduced into the reaction cavity in a pulse form, the pulse time is 4 s, and the carrier gas flow rate is 40 sccm;

[0069] S5, argon is introduced into the reaction cavity to purge excess tris(dimethylamine) cyclopentadienyl zirconium and reaction byproducts, and the purging time is 25 s;

[0070] S6, O3 is introduced into the reaction cavity in a pulse form, the pulse time is 0.1 s, the flow rate is 50 sccm, and an oxide film is generated;

[0071] S7, argon is introduced into the reaction cavity to purge excess O3 and reaction byproducts, and the purging time is 15 s;

[0072] S8, the steps S2-S7 are repeated for 200 cycles.

[0073] Example 3

[0074] The embodiment provides an application method of an organic small molecule inhibitor in thin film deposition, and the method comprises the following steps:

[0075] S1, a silicon wafer (aspect ratio of 30:1) is placed into an atomic layer deposition device, a reaction cavity heating temperature is 300 DEG C, and vacuum extraction is performed to 5 Pa;

[0076] S2, formamidine is placed in a stainless steel source bottle, the source bottle is connected with the reaction cavity of the atomic layer deposition device through a pipeline, a source bottle heating temperature is room temperature, a pipeline heating temperature is 150 DEG C, argon is used as a carrier gas, the formamidine is introduced into the reaction cavity in a pulse form, a pulse time is 0.05 s, and a carrier gas flow is 40 sccm;

[0077] S3, helium is introduced into the reaction cavity to purge excess formamidine, and a purging time is 15 s;

[0078] S4, tris (dimethylamine) cyclopentadienyl zirconium ([CpZr (NMe2) 3]) is placed in a stainless steel source bottle, the source bottle is connected with the reaction cavity through a pipeline, a source bottle heating temperature is 90 DEG C, a pipeline heating temperature is 150 DEG C, argon is used as a carrier gas, the tris (dimethylamine) cyclopentadienyl zirconium is introduced into the reaction cavity in a pulse form, a pulse time is 4 s, and a carrier gas flow is 40 sccm;

[0079] S5, argon is introduced into the reaction cavity to purge excess tris (dimethylamine) cyclopentadienyl zirconium and reaction by-products, and a purging time is 25 s;

[0080] S6, O3 is introduced into the reaction cavity in a pulse form, a pulse time is 0.1 s, a flow is 50 sccm, and an oxide thin film is generated;

[0081] S7, argon is introduced into the reaction cavity to purge excess O3 and reaction by-products, and a purging time is 15 s;

[0082] S8, steps S2-S7 are repeated for 200 cycles.

[0083] Example 4

[0084] The embodiment provides an application method of an organic small molecule inhibitor in thin film deposition, and the method comprises the following steps:

[0085] S1, a silicon wafer (aspect ratio of 30:1) is placed into an atomic layer deposition device, a reaction cavity heating temperature is 300 DEG C, and vacuum extraction is performed to 5 Pa;

[0086] 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 to room temperature, the pipeline is heated to 150 DEG C, argon is used as the carrier gas, and the hydroxyethyl urea is introduced into the reaction chamber in a pulse form, the pulse time is 0.3 s, and the carrier gas flow rate is 40 sccm;

[0087] S3, argon is introduced into the reaction chamber to purge excess hydroxyethyl urea, and the purging time is 15 s;

[0088] S4, tris(dimethylamine) 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 to 80 DEG C, the pipeline is heated to 150 DEG C, argon is used as the carrier gas, and the tris(dimethylamine) cyclopentadienyl hafnium is introduced into the reaction chamber in a pulse form, the pulse time is 0.5 s, and the carrier gas flow rate is 40 sccm;

[0089] S5, argon is introduced into the reaction chamber to purge excess tris(dimethylamine) cyclopentadienyl hafnium and reaction by-products, and the purging time is 25 s;

[0090] S6, O3 is introduced into the reaction chamber in a pulse form, the pulse time is 5 s, and the flow rate is 50 sccm;

[0091] S7, argon is introduced into the reaction chamber to purge excess O3 and reaction by-products, and the purging time is 15 s;

[0092] S8, the steps S2-S7 are repeated for 200 cycles.

[0093] Example 5

[0094] The 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 pulse time of alanine is 0.2 s, and the rest of raw materials and specific steps are the same as those in example 4.

[0095] Example 6

[0096] The 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 "N-hydroxyacetimidamide", the pulse time of N-hydroxyacetimidamide is 0.2 s, and the rest of raw materials and specific steps are the same as those in example 4.

[0097] Example 7

[0098] The 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 "N-hydroxyacetimidamide", the pulse time of N-hydroxyacetimidamide is 0.2 s, and the rest of raw materials and specific steps are the same as those in example 4.

[0099] S1, put the silicon wafer (aspect ratio 30:1) into the atomic layer deposition equipment, the reaction cavity heating temperature is 400℃, vacuum to 5Pa;

[0100] S2, put the aminourea into the stainless steel source bottle, the source bottle is connected with the reaction cavity of the atomic layer deposition equipment through the pipeline, the source bottle heating temperature is room temperature, the pipeline heating temperature is 150℃, use argon as the carrier gas, pulse the aminourea into the reaction cavity, the pulse time is 0.07s, the carrier gas flow is 100sccm;

[0101] S3, pulse the argon into the reaction cavity, purge the excess aminourea, the purge time is 15s;

[0102] S4, put the trimethoxy (pentamethylcyclopentadienyl) titanium ([Cp*Ti(OMe)3]) into the stainless steel source bottle, the source bottle is connected with the reaction cavity through the pipeline, the source bottle heating temperature is 90℃, the pipeline heating temperature is 150℃, use argon as the carrier gas, pulse the trimethoxy (pentamethylcyclopentadienyl) titanium into the reaction cavity, the pulse time is 0.15s, the carrier gas flow is 100sccm;

[0103] S5, pulse the inert gas into the reaction cavity, purge the excess trimethoxy (pentamethylcyclopentadienyl) titanium and the reaction byproducts, the purge time is 30s;

[0104] S6, pulse the O3 into the reaction cavity, the pulse time is 5s, the flow is 50sccm, generate the oxide film;

[0105] S7, pulse the argon into the reaction cavity, purge the excess O3 and the reaction byproducts, the purge time is 20s;

[0106] S8, repeat the steps S2-S7 for 200 cycles.

[0107] Example 8

[0108] The embodiment provides an application method of an organic small molecule inhibitor in thin film deposition, compared with example 7, the "aminourea" in example 7 is replaced by "isoleucine", the source bottle heating temperature of isoleucine is 30℃, the pulse time is 0.2s, and the rest of the raw materials and specific steps are the same as those in example 7.

[0109] Example 9

[0110] The embodiment provides an application method of an organic small molecule inhibitor in thin film deposition, compared with example 7, the "aminourea" in example 7 is replaced by "propylamidine", the pulse time of propylamidine is 0.3s, and the rest of the raw materials and specific steps are the same as those in example 7.

[0111] Comparative example 1

[0112] The comparative example provides a method for applying an organic small molecule inhibitor in thin film deposition. Compared with Example 1, steps S2 and S3 in Example 1 are removed, and the remaining raw materials and specific steps are the same as those in Example 1.

[0113] Comparative Example 2

[0114] The comparative example provides a method for applying an organic small molecule inhibitor in thin film deposition. Compared with Example 4, steps S2 and S3 in Example 4 are removed, and the remaining raw materials and specific steps are the same as those in Example 4.

[0115] Comparative Example 3

[0116] The comparative example provides a method for applying an organic small molecule inhibitor in thin film deposition. Compared with Example 7, steps S2 and S3 in Example 7 are removed, and the remaining raw materials and specific steps are the same as those in Example 7.

[0117] Comparative Example 4

[0118] The example provides a method for applying an organic small molecule inhibitor in thin film deposition. Compared with Example 1, “urea” in Example 1 is replaced with “triethylamine”, the pulse time of triethylamine is 0.2s, and the remaining raw materials and specific steps are the same as those in Example 1.

[0119] Comparative Example 5

[0120] The example provides a method for applying an organic small molecule inhibitor in thin film deposition. Compared with Example 4, “hydroxyethyl urea” in Example 4 is replaced with “ethylene glycol dimethyl ether”, the pulse time of ethylene glycol dimethyl ether is 0.2s, and the remaining raw materials and specific steps are the same as those in Example 4.

[0121] Comparative Example 6

[0122] The example provides a method for applying an organic small molecule inhibitor in thin film deposition. Compared with Example 7, “semicarbazide” in Example 7 is replaced with “tetrahydrofuran”, the pulse time of tetrahydrofuran is 0.02s, and the remaining raw materials and specific steps are the same as those in Example 7.

[0123] The deposited films obtained in Examples 1-9 and Comparative Examples 1-6 are detected, the film thickness at the top and bottom of the HAR substrate is measured by transmission electron microscopy, and then the step coverage is calculated. The instrument model is Talos F200X;

[0124] The step coverage calculation method is as follows:

[0125] The test results are shown in Table 1:

[0126] Table 1

[0127] From the recorded contents in Table 1, it can be seen that the step coverage obtained by the small molecule inhibitors used in Examples 1-9 is higher and the effect is better compared to the use of no inhibitor in Comparative Examples 1-3 and the small molecule inhibitors (triethylamine, ethylene glycol dimethyl ether, tetrahydrofuran) used in Comparative Examples 4-6, proving that compared to the reported inhibitor molecules, the molecular structure of the inhibitors of the present application has two or more than two N, O atoms, which can form multiple hydrogen bonds, and has a better inhibiting effect, inhibiting the growth of the top film, the bottom growth is not inhibited or the inhibiting effect is weak, significantly improving the step coverage, and eliminating the formation of joints or voids in the gap filling process.

[0128] It should be noted that the relational terms herein such as first and second and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any such actual relationship or order between such entities or actions. Moreover, the terms "comprises", "comprising", or any other variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0129] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and variations can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. An organic small molecule inhibitor, characterized in that Including urea compounds, amino acid compounds and amidine compounds.

2. An organic small molecule inhibitor according to claim 1, characterized in that Urea compounds have the structure shown in Formula I: In Formula I, R1, R2, R3, and R4 are each independently selected from the group consisting of: Any group substituted by hydrogen, halogen, or heteroatom; any group substituted by heteroatom includes optionally substituted aliphatic, optionally substituted cycloaliphatic or heterocycloaliphatic, and optionally substituted aromatic, wherein the heteroatom is one or more of O, N, S, P, B, and Si.

3. An organic small molecule inhibitor according to claim 1, characterized in that: The urea compound is one of urea, hydroxyethyl urea and semicarbazide.

4. An organic small molecule inhibitor according to claim 1, characterized in that: The amino acid compound has the structure shown in Formula II: In Formula II, R1 and R2 are each independently selected from the group consisting of: Any group substituted by hydrogen, halogen, or heteroatom; any group substituted by heteroatom includes optionally substituted aliphatic, optionally substituted cycloaliphatic or heterocycloaliphatic, and optionally substituted aromatic; the heteroatom is one or more of O, N, S, P, B, and Si.

5. An organic small molecule inhibitor according to claim 1, characterized in that: The amino acid compound is one of glycine, alanine and isoleucine.

6. An organic small molecule inhibitor according to claim 1, characterized in that: The amidine compound has the structure shown in Formula III: In Formula III, R1, R2, R3, and R4 are each independently selected from the group consisting of: Any group substituted by hydrogen, halogen, or heteroatom; any group substituted by heteroatom includes optionally substituted aliphatic, optionally substituted cycloaliphatic or heterocycloaliphatic, and optionally substituted aromatic; the heteroatom is one or more of O, N, S, P, B, and Si.

7. The organic small molecule inhibitor according to claim 1, characterized in that: The amidine compound is one of N,N'-diisopropyl-formamidine, N,N'-diisopropyl-acetamidine, N,N'-diisopropyl-propionamidine, N-hydroxyacetamidine, formamidine, acetamidine and propionamidine.

8. Use of the organic small molecule inhibitor according to any one of claims 1 to 7 in HAR substrate thin film deposition on a high aspect ratio substrate.

9. The method for applying an organic small molecule inhibitor in thin film deposition according to claim 8, 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. Place the organic small molecule inhibitor in a stainless steel source bottle and connect it to the reaction chamber. Heat the source bottle to 30-100°C and the pipeline to 50-150°C. Use an inert gas as a carrier gas and introduce the organic small molecule inhibitor into the reaction chamber in a pulsed manner. S3, introduce inert gas into the reaction chamber, purge time 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 a temperature of 30-100 ° C, the pipeline is heated at a temperature of 50-150 ° C, and an inert gas is used as a carrier gas. The precursor is introduced into the reaction chamber in a pulsed form; S5. Introduce inert gas into the reaction chamber for 5-50 seconds; S6. Introduce an oxygen source into the reaction chamber in a pulsed manner 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 5-50s; 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.

10. The method for applying an organic small molecule inhibitor in thin film deposition according to claim 9, characterized in that: The precursor is a Si-based precursor or a metal-based precursor.

Images