KR20120056813A - Precursors for cvd silicon carbo-nitride films - Google Patents

Abstract

PURPOSE: A precursor for a CVD(Chemical Vapor Deposition) silicone carbon-nitride film is provided to remove undesirable silicon dioxide by maintaining low etching speed. CONSTITUTION: A method for forming a dielectric film through a deposition process is as follows. A substrate is placed in a deposition chamber. Amino-silane or their mixture are injected into the deposition chamber. A nitrogen source, an oxidizing agent, or their mixture are injected into the deposition chamber, wherein the nitrogen source is selected from the group consisting of hydrazine, dimethylhydrazine, nitrogen, and ammonia and the oxidizer is selected from the group consisting of oxygen, hydrogen peroxide, ozone, and nitrogen oxide. A dielectric film is formed on the substrate through reaction of the nitrogen source or oxidizer with the amico-silane.

Description

Precursor for COD silicon carbonitride film {PRECURSORS FOR CVD SILICON CARBO-NITRIDE FILMS}

In the manufacture of semiconductor devices, a thin passivation layer of chemically inert dielectric material such as silicon nitride (Si ₃ N ₄ ) or silicon carbonitride (Si _x C _y N _z ) is essential. A thin layer of silicon nitride acts as a diffusion mask, an oxide barrier, trench isolation, an intermetallic dielectric material with a high dielectric breakdown voltage and a protective film layer.

Many applications for silicon nitride coatings in the manufacture of semiconductor devices are known, and are compiled by Gary E. McGuire, Semiconductor and Process Technology Handbook, Noyes Publication, New Jersey, (1988), pp 289- 301; And Silicon Processing for the VLSI ERA, Wolf, Stanley and Talbert, Richard N., Lattice Press, Sunset Beach, Calif. (1990), pp 20-22, 327-330.

Many new semiconductor devices require dielectric films having very low etch rates or very high film stresses, or both. In addition, the film is preferably formed at temperatures below 600 ° C. while maintaining good electrical properties and is sometimes necessary. Film hardness is another factor to consider in the design of electrical components and silicon nitride films provide very rigid films.

One commercial method of forming a silicon nitride coating uses dichlorosilane and ammonia as precursor reactants. Low pressure chemical vapor deposition (LPCVD) using precursors such as dichlorosilane and ammonia requires high deposition temperatures to obtain the best film properties. For example, temperatures above 750 ° C. may be required to obtain adequate growth rates and uniformity. Other process issues include the risk of chlorine and chlorine by-products.

The following papers and patents are cited as representative references in the field of synthesis and deposition processes for organosilanes used in the electronics industry.

Aethyl Hochberg and DL O'Meara, Diethylsilane as Silicon Source for the Deposition of Silicon Nitride and Silicon Nitride Nitride Films by LPCVL as a Silicon Source for the Deposition of Silicon Nitride and Silicon Oxynitride Films By LPCVD ), Mat. Res. Soc. Symp. Proc., Vol. 204, (1991), pp 509-514 disclose the formation of silicon nitride and silicon oxynitride films using diethylsilane with ammonia and nitrogen oxides by LPCVD. Deposition is carried out in a temperature range of 650 to 700 ° C. Deposition is generally limited to temperatures of 650 ° C. as the deposition rate drops to 4 ANG./min at lower temperatures.

Sorita et al., Si ₃ N ₄ derived from SiH ₂ Cl ₂ and NH ₃ A low-pressure mass analysis and study the reaction speed of the chemical vapor deposition of a thin film (Mass Spectrometric and Kinetic Study of Low - Pressure Chemical Vapor Depositoin of Si ₃ N ₄ Thin Films From SiH ₂ Cl ₂ and NH ₃ ), J. Electro. Chem. Soc., Vol. 141, No. 12, (1994), pp 3505-3511 describe the deposition of silicon nitride using dichlorosilane and ammonia using the LPCVD process. The formation of ammonium chloride causes particle formation and deposition of ammonium chloride in the back of the tube and in piping lines and pump systems.

Aylett and Emsley, Preparation and Properties of Dimethylamino and Diethylamino Silane (The Preparation and Properties of Dimethylamino and Diethylamino Silane), J. Chem. Soc. (A) p 652-655, 1967 disclose the reaction of iodosilane with each dialkyl amine to produce dimethylamino and diethylaminosilane.

Anderson and Rankin, isopropyldisylylamine and disylyl- t- butylamine : gas phase molecular structure determined by preparation, spectroscopic properties and electron diffraction ( Isopropyldisilylamine and Disilyl -t- butylamine : Preparation , Spectroscopic Properties , and Molecular Structure in the Gas Phase , Determined by Electron Diffraction ), J. Chem. Soc. Dalton Trans., P 779-783 (1989) discloses the synthesis of disilyl amines of the formula NR (SiH ₃ ) ₂ , for example isopropyldiylylamine and disilyl-t-butylamine, and the corresponding methyldi A spectroscopic comparison is given to silylamine.

Japanese Patent 6-132284 discloses a general formula (R ₁ R ₂ N) _n SiH _{4 -n} (R ₁ and R ₂ is H-CH) by either plasma enhanced chemical vapor deposition or thermal chemical vapor deposition in the presence of ammonia or nitrogen. _3- , C ₂ H ₅ -C ₃ H _7- , C ₄ H ₉ -It is described the formation of a silicon nitride film using an organosilane.

U.S. Patent 5,234,869 discloses the formation of silicon nitride films by CVD using Si (N (CH ₃ ) ₂ ) ₄ and ammonia as reactant gases. A chamber temperature of 700 ° C. and a pressure of 0.5 Torr were used for the deposition. Other reactants also selected from the group consisting of SiH (N (CH ₃ ) ₂ ) ₃ , SiH ₂ (N (CH ₃ ) ₂ ) _2, and SiH ₃ (N (CH ₃ ) ₂ ), in combination with ammonia or nitrogen, are also reactants. As presented. It is also disclosed that the plasma produced by radiating the gas with ultraviolet rays, the temperature was reduced to 300 ℃.

U.S. Patent 5,874,368 discloses the use of bis (tertbutylamino) silane as a precursor for depositing silicon nitride using low pressure chemical vapor deposition in the temperature range of 500 to 800 ° C.

U.S. Patent 5,874,368 and U.S. Patent 6,153,261 disclose the formation of a silicon nitride film using bis (tertbutylamino) silane as the silicon reactant gas. LPCVD is used for film production.

U.S. Patent 6,391,803 discloses the formulas Si (N (CH ₃ ) ₂ ) ₄ , SiH (N (CH ₃ ) ₂ ) ₃ and SiH ₂ (N (CH ₃ ) ₂ ) ₂ , SiH ₃ (N (CH ₃ ) ₂ ) The formation of silicon comprising thin films by atomic layer deposition using silane, preferably trisdimethylaminosilane as the first reactant, is disclosed. Part of the first reactant is chemically adsorbed on the substrate and the second part is physically adsorbed on the substrate. The reactant is removed and a second reactant, NH _3, is introduced.

A class of liquid aminosilanes has been found that allows CVD processes to produce silicon carbonitride films of the general formula Si _x C _y N _z . These aminosilanes, unlike some precursors previously used, are liquid at room temperature and at pressures that allow for convenient handling. The invention also relates to a deposition method for producing such a film.

The class of compounds and mixtures thereof is generally represented by the formula:

Wherein R is selected from saturated or unsaturated, straight, branched or cyclic C ₁ -C ₁₀ alkyl group, aromatic, heterocyclic or in the case of formula C, R ¹ is saturated or unsaturated, with or without substituents Selected from a straight, branched or cyclic C ₂ -C ₁₀ alkyl group, aromatic, heterocyclic, hydrogen, silyl group, R and R ¹ in formula (A) may be bonded to a cyclic group (CH ₂ ) _n , n Is 1-6, preferably 4 and 5, and R ² represents a single bond, a (CH ₂ ) _n chain, a ring, SiR ₂ , or SiH ₂ . Preferred compounds are those in which both R and R ₁ have two or more carbon atoms.

Precursors used in CVD processes can achieve a number of advantages, including:

The ability to facilitate the formation of a dielectric film without causing problems of plasma deposition at low temperature conditions;

The ability to mix aminosilanes with other precursors such as ammonia at various stoichiometry to control the ratio of Si-C bonds to Si-N bonds and thereby control the properties of the resulting film;

The ability to produce films with high refractive indices and film stresses;

The ability to produce films with low etch rates;

The ability to produce high density films;

The ability to produce films while avoiding chlorine contamination; And

The ability to operate at low pressures (20 mTorr to 2 Torr) in a manufacturable batch furnace (100 wafers or more); And

Ability to produce Si _x C _y N _z films at low temperatures, for example 550 ° C. and below.

It has been found that a class of liquid organic aminosilanes with N-SiH ₃ groups as the main feature of the molecular structure is suitable as precursor for producing silicon carbonitride films via CVD in the electronics industry. These compounds enable the production of Si _x C _y N _z films under various conditions.

The compounds of the present invention are liquid at atmospheric pressure and room temperature, ie 25 ° C. and thus provide important advantages in the reported use of trimethyl substituted aminosilanes. These are substituted with organic groups having two or more carbon atoms in the chain on the amino group which provide stability under normal handling and processing conditions.

The first class of aminosilanes is represented by Formula A:

R in this class of compounds is selected from saturated or unsaturated, straight chain, branched chain or cyclic C ₁ -C ₁₀ alkyl groups, aromatics, heterocyclics. R ¹ is selected from saturated or unsaturated, straight, branched or cyclic C ₂ -C ₁₀ alkyl group, aromatic, heterocyclic, hydrogen, silyl group with or without substituents, and R and R ¹ are bonded to a cyclic group May be Typical substituents are cyclic alkyl groups such as ethyl and especially including its isomers, propyl and butyl and C _{2 -4} alkyl group such as, cyclopropyl, cyclopentyl and cyclohexyl. Some examples of preferred compounds of this class are represented by the formula:

N is 1-6 in formula, Preferably it is 4 or 5.

The second class of aminosilanes has two silyl groups attached to one nitrogen atom, as represented by the following formula (B).

Like the R groups of the first class of compounds, R is selected from saturated or unsaturated, straight, branched or cyclic C ₁ -C ₁₀ alkyl groups, aromatics, heterocyclics. Specific R groups are methyl, ethyl, propyl, allyl, and butyl; And cyclic groups such as cyclopropyl, cyclopentyl, and cyclohexyl. Examples of compounds are represented by the formula:

The third class of aminosilane compounds is represented by the formula (C) below. These are generally diaminodiylyl compounds in which R is the same as R and R ¹ in formula A and the R ² groups serve as crosslinking of the nitrogen atoms. Often R ² groups are only single bonds between nitrogen atoms or may be crosslinked groups such as SiR ₂ , SiH ₂ , chains or rings. The chemical formula is:

Specific examples include those represented by the following formula:

These compounds are generally synthesized by the following reactions, which are also described in Examples 1,2,3 and 4.

This series of reactions illustrates the route to the aminosilanes described above, but other sources of silane precursors may also be used. This route enables the use of various types of amines and straight forward control as to whether mono and disylyl compounds are prepared using reaction stoichiometry.

In addition, some of these compounds, Preparation and Properties of Dimethylamino and Diethylamino Silane (The Preparatoin and Properties of Dimethylamino and Diethylamino Silane , Aylett and Emsley, J. Chem. Soc. (A) p 652-655, 1967), may also be synthesized by reaction of the corresponding amine with monohalosilane.

XSiH ₃ + 2 RR ¹ NH-> RR ¹ N-SiH ₃ + RR ¹ NH. HX

Representative amines well suited for this reaction are alkyl, cyclic, and heterocyclic. Preferred amines are lower alkyl amines such as ethyl, iso-propyl, t-butyl, and cyclohexyl. The amine may also be primary or secondary, depending on the desired product.

In the formation of silicon carbonitride films, optionally mono or diaminosilane with ammonia or nitrogen sources are allowed to react in the deposition chamber at conventional deposition temperatures. Such films may be formed in deposition chambers designed for chemical vapor deposition (CVD), low pressure chemical vapor deposition (LPCVD), plasma enhanced CVD (PECVD), atomic layer deposition (ALD), and the like. The term CVD as used herein is meant to encompass each of these processes used in semiconductor deposition.

As noted in the advantages, the liquid aminosilanes described herein in many cases provide the manufacturer with the ability to form silicon carbonitride films through CVD at relatively low temperatures, even though the general temperature range is from 500 to 700 ° C. Unexpectedly, Si _x C _y N _z film deposition can possibly be due to the high activity of the SiH ₃ groups. It is believed that the low steric hindrance of the ammonia amino group transfer reaction at the center of silicon causes these compounds to react with ammonia and deposit films at increasing nitrogen concentrations at relatively low temperatures.

Deposition of the aminosilane precursor may be performed in the presence or absence of an active nitrogen source such as hydrazine, dimethylhydrazine, or ammonia. The molar ratio of nitrogen source to aminosilane is generally present in a wide range from 0: to 10: 1. The upper limit is limited by the dilution effect on the precursor and the dilution effect will significantly reduce the deposition rate. Preferred ranges are from 0.1 to 4: 1. Formation of the film through deposition may be performed with or without other gases, including inert gases such as nitrogen and helium. The use of gas by the manufacturer to achieve dilution of the corresponding precursors can improve the conformality of the deposition or improve the penetration for chemical vapor penetration.

Low pressure chemical vapor deposition (LPCVD) involves chemical reactions that can occur on various substrates, such as silicon, within a pressure range of 20 mTorr to 20 Torr. High pressure CVD can cause gas phase nucleation or predeposition before the desired substrate is reached. Dilution of the aminosilane precursor may be required in such high pressure reactions. Low pressure deposition with some aminosilane precursors can exhibit deposition rates of non-chemically available levels. However, such aminosilanes may be suitable for atomic layer deposition.

In carrying out the deposition process, the aminosilanes described herein may be mixed with other silyl precursors to alter film properties. Examples of other precursors include bis-tert-butylaminosilane, tris-iso-propylaminosilane, bis-diethylaminosilane, tris-dimethylaminosilane and bis-iso-propylaminosilane.

A class of liquid aminosilanes has been found that allows CVD processes to produce silicon carbonitride films of the general formula Si _x C _y N _z . These aminosilanes, unlike some precursors previously used, are liquid at room temperature and at pressures that allow for convenient handling. The present invention also provides a deposition method for producing such a film.

1 is a curve of the stress values of a film formed by deposition of diethylaminosilane and bis (tert) butylaminosilane as a function of the molar ratio of NH ₃ to precursor during the deposition process.
2 is a curve of the hardness of a film formed by the deposition of diethylaminosilane and bis (tert) butylaminosilane as a function of temperature during the deposition process for standard SiO ₂ .
3 is diethylaminosilane (neat), NH ₃ And infrared spectral ions of the film produced by the deposition of diethylaminosilane and bis (tert) butylaminosilane.

The following examples are intended to illustrate various embodiments of the invention, including the synthesis of various silanes and LPCVD of silicon carbonitride film forming precursors.

Example 1 Synthesis of Diethylaminosilane

50 g (0.33 mol) of trifluoromethanesulfonic acid and 100 ml of toluene were added to a 250 ml flask. Under the protection of nitrogen, the flask was cooled to -40 ° C. 40.6 g (0.33 mol) of tolylsilane was added slowly. The flask was then cooled to -60 ° C. 33.5 g of triethylamine were added slowly, followed by 24 g of diethylamine. After addition, the flask was allowed to slowly warm to room temperature. Two layers of liquid formed. The upper layer was separated using a separatory funnel. 25 g of diethylaminosilane was obtained by vacuum distillation. The boiling point of diethylaminosilane was 40-42 ° C. at 210 mmHg.

Example 2 Synthesis of Di-iso-propylaminosilane

50 g (0.33 mol) of trifluoromethanesulfonic acid and 80 ml of pentane were added to a 250 ml flask. Under the protection of nitrogen, the flask was cooled to -40 ° C. 35.6 g (0.33 mol) of phenylsilane were added slowly. The flask was then cooled to -60 ° C. 33.3 g (0.33 mole) of triethylamine was added slowly, followed by 33.3 g (0.33 mole) of di-iso-propylamine solution in 15 ml of pentane. After addition, the flask was allowed to slowly warm to room temperature. Two layers of liquid formed. The upper layer was separated using a separatory funnel. Solvent and byproduct benzene were removed by distillation. 30 g of di-iso-propylaminosilane was obtained by vacuum distillation. The boiling point of di-iso-propylaminosilane was 55 ° C. at 106 mmHg.

Example 3 Synthesis of Cyclohexyldisylylamine and 2,4-Dicyclohexyl-2,4-diaza-1,3,5-trisilapentane

62.5 g of trifluoromethanesulfonic acid and 100 ml of pentane were added to a 500 ml flask. Under the protection of nitrogen, the flask was cooled to -40 ° C. 45 g of phenylsilane was added slowly. The flask was then cooled to -60 ° C. 42 g of triethylamine were added slowly, followed by 20.6 g of cyclohexylamine solution in 15 ml of pentane. After addition, the flask was allowed to slowly warm to room temperature. Two layers of liquid formed. The upper layer was separated using a separatory funnel. Solvent and byproduct benzene were removed by distillation. 15 g of cyclohexyldisylylamine was obtained by vacuum distillation. The boiling point of cyclohexyldisilylamine was 54-55 ° C. at 17 mmHg. The remaining high boiling point portion contains 96.6% 2,4-dicyclohexyl-2,4-diaza-1,3,5-trisilapentane.

Example 4 Synthesis of t-butyldisilylamine and 2,4-di-tert-butyl-2,4-diaza-1,3,5-trisilapentane

50.0 g (0.33 mol) of trifluoromethanesulfonic acid and 100 ml of pentane were added to a 500 ml flask. Under the protection of nitrogen, the flask was cooled to -40 ° C. 35.6 g (0.33 mol) of phenylsilane were added slowly. The flask was then cooled to -60 ° C. 33.3 g (0.33 mole) of triethylamine were added slowly, followed by 28.7 g (0.165 mole) of t-butylamine solution in 15 ml of pentane. After addition, the flask was allowed to slowly warm to room temperature. Two layers of liquid formed. The upper layer was separated using a separatory funnel. Solvent and byproduct benzene were removed by distillation. 21 g of 2,4-di-tert-butyl-2,4-diaza-1,3,5-trisilapentane were obtained by vacuum distillation.

Example 5 Formation of Silicon Carbonitride Film Using Diethylaminosilane Precursor

General process

Aminosilane precursors are tested in LPCVD reactors used to impart precursor qualification for experiments for silicon carbonitride deposition. The precursor is degassed and metered into the reactor via the required low pressure mass flow controller (MFC). MFC flow rate was determined by weight loss vs. chemical weight. Adjust for flow time. Characterized further reactants, such as ammonia, and diluents, such as nitrogen and helium, are also metered into the reactor through the adjusted MFC as required. The reactor is connected to a roots blower / dry pump combination that can degas the reactor below 10 ^-4 Torr (0.013 Pa). During deposition, the temperature over the load of the silicon wafer is within 1 ° C. of the set point.

Silicon wafers are loaded onto a quartz boat and injected into the reactor. The reactor pumps to base pressure and checks for leaks. The system increases to the process temperature with a gas stream that dilutes any residual oxygen or moisture to prevent oxidation of the silicon wafer as the reactor is heated. The reactor is then stabilized for a predetermined time period where all wafer surfaces are at the same temperature (as determined by preliminary measurements on the wafer with attached thermocouples).

Gas and vapor are injected into the reactor for a predetermined deposition time at a controlled pressure. Then the gas is shut off and the reactor is pumped to the basal pressure. Then as the reactor cools, it is pump-purged, pumped down, and pump-purged to purge any reactive gases or vapors. Backfill the reactor to atmospheric pressure; The wafer is removed and allowed to cool to room temperature. The film thickness, film refractive index, film stress (FIG. 1), infrared absorbance (shown in FIG. 3), dielectric constant and acid etch rate (Table 1) of the deposited film were then measured.

In the formation of the deposited film, 10 sccm of diethylaminosilane (DEAS) was introduced into the reactor at 570 ° C. for 60 minutes deposition time at 1.3 Torr (173.3 Pa) with 20 sccm NH ₃ and 20 sccm N _2. .

The average film thickness was 69 nm and refractive index was 2.045. Film stress was measured to 1.07 × 10 ¹⁰ dynes / cm ² (1.07 GPa).

Infrared spectra showed significant Si-C and Si-N absorption. CH or CN absorption was in the noise display as shown in FIG. 3 and the film composition was mainly in the form of Si _x C _y N _z as desired.

Example 6 Formation of Silicon Carbonitride Film Using N ₂ without NH ₃ and Using Diethylaminosilane Precursor

The procedure of Example 5 was followed except for the process conditions. Nitrogen was used instead of NH ₃ . In this example, 10 sccm of diethylaminosilane (DEAS) was introduced into the reactor at 600 ° C. for 40 minutes of deposition time at 1.0 Torr (133 Pa) with 40 sccm N ₂ .

The average film thickness was 42 nm and refractive index was 2.288. Film stress was measured at 1.34 × 10 ¹⁰ dynes / cm ² (1.07 GPa). These films have higher stresses and lower etch rates than those obtained with ammonia (see Table 1 for etch rates). The uniformity of such films was found to be 100% on isolated structures.

Example 7 Formation of Silicon Carbonitride Film Using N ₂ without NH ₃ and Using Diisopropylaminosilane Precursor

The procedure of Example 5 is followed except for the precursor. 10 sccm of diisopropylaminosilane (DIPAS) was introduced into the reactor at 570 ° C. with a deposition time of 70 minutes at 1.0 Torr (133 Pa) with 20 sccm He and 20 sccm N ₂ .

The average film thickness was 46 nm and refractive index was 2.056. Film stress was measured to 1.07 × 10 ¹⁰ dynes / cm ² (1.07 GPa). Surprisingly, the refractive index and stress for diisopropylaminosilane were similar to those of the precursor of Example 6. These results indicate that good stress values can be achieved in this class of materials.

Example 8 Formation of Silicon Carbonitride Film Using N ₂ without NH ₃ and Bis (tertiary Butylamino) silane Precursor as Control

The procedure of Example 5 was followed except for the precursor, which was used as a control. BTBAS is a precursor used in production worldwide and has been selected as a representative aminosilane comparison because of its well recognized performance characteristics.

10 sccm of bis (tertiary butylaminosilane (BTBPAS) was introduced into the reactor at 570 ° C. for 70 minutes of deposition time at 1.0 Torr (133 Pa) with 20 sccm He and 20 sccm N ₂ . It has only 20% stress and less than 10% etch resistance of the aminosilane (see Table 1).

1 was generated using stress data for bis (tert) butylaminosilane and diethylaminosilane. This represents the result of the stress measurement using the FSM system. The results for diethylaminosilane were unexpected, ie high stresses were achieved at low NH ₃ : DEAS ratios, including maintenance of high stress at moderate NH ₃ : DEAS ratios.

Precursors, such as bis (tertbutylamino) silane and dichlorosilane, produce films with stresses that decrease as the ammonia ratio to chemicals decreases. At low NH ₃ : BTBAS ratios the stress results are not good. Decreasing ammonia for these precursors results in silicon-rich films that reduce the coefficient of thermal expansion of these films relative to the silicon substrate. While not wishing to be bound by theory, the decreasing ammonia: DEAS ratio in the deposition process increases the Si to N atomic ratio and the effect is to increase the C to Si atomic ratio. Apparently some Si—N are then replaced with Si—C bonds, which lead to the creation of films with similar stresses.

The second component of the example was the measurement of film hardness. This was measured by indentation using a Hysitron system. 2 is a curve showing deposited film hardness. When diethylaminosilane was used as the precursor, a harder film was obtained compared to BTBAS deposition and thermally grown silicon dioxide. Harder films further protect the underlying layers and themselves in chemical-mechanical polishing (CMP) operations. This property was also surprising.

Example 9 Etch Resistance of Silicon Nitride and Silicon Carbonitride Films

In this example, the etching results of various silicon nitrides and silicon carbonitrides are listed in Table 1. Table 1 shows the results of etch films from various precursors in 1% (in 49%) HF. Etch rates are shown relative to the value of thermally grown silicon dioxide etched at the same time. The lower the etch rate, the better it is to maintain its appearance and to protect the underlying layer as unwanted silicon dioxide is removed.

Comparison of Film Etch Rate at 1% in 49% HF at 24 ° C chemical substance NH ₃ rain Deposition temperature ℃ 1% HF etch rate for SiO ₂ BTBAS 2: 1 570 0.188 BTBAS 0 570 0.018 DEAS 2: 1 570 0.006 DEAS 4: 1 570 0.008 DEAS 1: 1 570 0.009 DEAS 0 570 0.001 DIPAS 2: 1 570 0.006 DIPAS 0 570 0.006 BTBAS = bis (tertbutylamino) silane DEAS = diethylaminosilane DIPAS = diisopropylaminosilane

From Table 1 above, DEAS at an NH ₃ to precursor ratio of 0 to 2 appears to have a good low etch rate. On the other hand, the ratio NH ₃ : BTBAS showed a higher etch rate than DEAS at a 2: 1 ratio even at 0.0: 1. Note that good low etch rates are seen at low NH ₃ : BTBAS ratios, but BTBAS stress levels are poor at low NH ₃ : BTBAS levels.

In summary, dielectric silicon carbonitride films of the formula Si _x C _y N _z can be prepared from the class of aminosilanes described above by CVD and other deposition processes. While many precursors for Si _x C _y N _z film formation do not perform well, it is believed that the high activity of SiH ₃ groups leads to Si _x C _y N _z film deposition at temperatures as low as 550 ° C.

It is also believed that the low steric hindrance of the ammonia amino group transfer reaction in the silicon center causes these compounds to react with ammonia and form films with increasing nitrogen concentrations at relatively low temperatures. Ligands such as ethyl, isopropyl, butyl and the like act as good leaving groups because they are volatile byproducts by beta-hydride removal. Any carbon left behind is bonded to silicon. On the other hand, aminosilane precursors having methyl groups as known in the past do not have this separation path. They remain bound to nitrogen and can be contained and trapped in the growing film. The presence of such trapped methyl groups is readily identified in the infrared spectrum (see FIG. 3). The absence of the C-H peak in FIG. 3 here indicates that the trapped hydrocarbons in the film can be at extremely low levels.

Claims (96)

Providing a substrate in a deposition chamber,
Introducing an aminosilane represented by Formula A, B or C or a mixture thereof into the deposition chamber, and
The nitrogen source or oxidant is introduced into the deposition chamber by introducing a nitrogen source selected from the group consisting of hydrazine, dimethyl hydrazine, nitrogen and ammonia, or an oxidant selected from the group consisting of oxygen, hydrogen peroxide, ozone and nitrogen monoxide into the deposition chamber. Reacting to provide a dielectric film on the substrate
Method of forming a dielectric film through a deposition process comprising a.

(Of the above formulas,
R is selected from straight, branched or cyclic saturated or unsaturated C ₁ -C ₁₀ alkyl groups, aromatic groups, heterocyclic groups and amine groups, but R in Formula C may further be a silyl group,
R ¹ is selected from branched or cyclic saturated or unsaturated C ₃ -C ₁₀ alkyl groups, aromatic groups, heterocyclic groups and hydrogen,
Wherein R and R ¹ in Formula A may be bonded to a cyclic group, R and other R in Formula C may be bonded to a cyclic group,
R ² is a single bond, (CH ₂ ) _n chain (n is 1-6), a ring, SiR ₂ or SiH ₂ ,
Provided that both R and R ^{1 in} formula A are not straight chain alkyl groups, isopropyl or isobutyl.) The method of claim 1, wherein the temperature of the substrate during deposition is in the range of about 500 to 700 ° C. 3. The method of claim 1, wherein the pressure during deposition is in the range of about 20 mTorr to 20 Torr. The method of claim 1, wherein the deposition process is one or more selected from chemical vapor deposition, low pressure chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition. The method of claim 4, wherein the deposition process is chemical vapor deposition. The method of claim 4, wherein the deposition process is atomic layer deposition. The method of claim 1, further comprising introducing an inert gas into the deposition chamber. The precursor according to claim 1, wherein the precursor is selected from the group consisting of bis-tert-butylaminosilane, tris-iso-propylaminosilane, bis-diethylaminosilane, tris-dimethylaminosilane and bis-iso-propylaminosilane. Introducing into the deposition chamber. The method of claim 1 wherein the molar ratio of nitrogen source to aminosilane is in the range of 0.1 to 10: 1. The method of claim 9 wherein the nitrogen source is ammonia or nitrogen and the molar ratio of nitrogen source to aminosilane is from 0.1 to 4: 1. The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

Where n is 1-6 The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

The method according to any one of claims 1 to 10, wherein the aminosilane is represented by the following formula.

A dielectric film deposition composition comprising an aminosilane represented by the following formula (A), (B) or (C) or a mixture thereof.

(Of the above formulas,
R is selected from straight, branched or cyclic saturated or unsaturated C ₁ -C ₁₀ alkyl groups, aromatic groups, heterocyclic groups and amine groups, but R in Formula C may further be a silyl group,
R ¹ is selected from branched or cyclic saturated or unsaturated C ₃ -C ₁₀ alkyl groups, aromatic groups, heterocyclic groups and hydrogen,
Wherein R and R ¹ in Formula A may be bonded to a cyclic group, R and other R in Formula C may be bonded to a cyclic group,
R ² is a single bond, (CH ₂ ) _n chain (n is 1-6), a ring, SiR ₂ or SiH ₂ ,
Provided that both R and R ^{1 in} formula A are not straight chain alkyl groups, isopropyl or isobutyl.) 33. The composition of claim 30, further comprising a nitrogen source selected from the group consisting of hydrazine, dimethyl hydrazine, nitrogen and ammonia. 31. The composition of claim 30, further comprising an oxidant selected from the group consisting of oxygen, hydrogen peroxide, ozone and nitrogen monoxide. The precursor of claim 30 wherein the precursor is selected from the group consisting of bis-tert-butylaminosilane, tris-iso-propylaminosilane, bis-diethylaminosilane, tris-dimethylaminosilane and bis-iso-propylaminosilane. The composition further comprises. The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

Where n is 1-6 The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:
The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

The composition according to any one of claims 30 to 33, wherein the aminosilane is represented by the formula:

An aminosilane compound having the formula A, B or C, which is liquid at room temperature and pressure.

(Of the above formulas,
R is selected from straight, branched or cyclic saturated or unsaturated C ₁ -C ₁₀ alkyl groups, aromatic groups, heterocyclic groups and amine groups, but R in Formula C may further be a silyl group,
R ¹ is selected from branched or cyclic saturated or unsaturated C ₃ -C ₁₀ alkyl groups, aromatic groups, heterocyclic groups and hydrogen,
Wherein R and R ¹ in Formula A may be bonded to a cyclic group, R and other R in Formula C may be bonded to a cyclic group,
R ² is a single bond, (CH ₂ ) _n chain (n is 1-6), a ring, SiR ₂ or SiH ₂ ,
Provided that both R and R ^{1 in} formula A are not straight chain alkyl groups, isopropyl, isobutyl, or phenyl, and R in formula B is not methyl, isopropyl, tert.butyl, or phenyl, and is different from R in formula C. R is not a silyl group when R ² represents a single bond.) The aminosilane compound of claim 53 having the formula

The aminosilane compound of claim 53 having the formula

The aminosilane compound of claim 53 having the formula

The aminosilane compound of claim 53 having the formula

The aminosilane compound of claim 53 having the formula

The aminosilane compound of claim 53 having the formula

Where n is 1-6 The aminosilane compound of claim 53 having the formula

The aminosilane compound of claim 53 having the formula

The aminosilane compound of claim 53 having the formula

The aminosilane compound of claim 53 having the formula

The aminosilane compound of claim 53 having the formula

The aminosilane compound of claim 53 having the formula

The aminosilane compound of claim 53 having the formula

The aminosilane compound of claim 53 having the formula

The aminosilane compound of claim 53 having the formula

The aminosilane compound of claim 53 having the formula

Providing a reaction mixture comprising arylsilane and sulfonic acid such that arylsilane and sulfonic acid react to form an intermediate; And
Adding an amine selected from the group consisting of secondary amines and primary amines to the reaction mixture such that the amines react with intermediates to provide aminosilanes having the formulas A, B or C
Method for producing an aminosilane represented by the following formula A, B or C comprising a.

(Of the above formulas,
R is selected from straight, branched or cyclic saturated or unsaturated C ₁ -C ₁₀ alkyl groups, aromatic groups, heterocyclic groups and amine groups, but R in Formula C may further be a silyl group,
R ¹ is selected from branched or cyclic saturated or unsaturated C ₃ -C ₁₀ alkyl groups, aromatic groups, heterocyclic groups and hydrogen,
Wherein R and R ¹ in Formula A may be bonded to a cyclic group, R and other R in Formula C may be bonded to a cyclic group,
R ² is a single bond, (CH ₂ ) _n chain (n is 1-6), a ring, SiR ₂ or SiH ₂ ) The method of claim 70, wherein the reaction mixture further comprises a solvent, and further comprising separating the aminosilane having Formula A, B, or C from the reaction mixture. The method of claim 70, wherein the reaction mixture further comprises triethylamine. The method of claim 70, wherein the reaction mixture is cooled to −40 ° C. or less prior to addition of the amine. The method of claim 70, wherein the arylsilane is selected from the group consisting of phenylsilane and tolylsilane. The method of claim 70, wherein the sulfonic acid is trifluoromethanesulfonic acid. 78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

Where n is 1-6 78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

78. The method of any one of claims 70-75, wherein the aminosilane is represented by the formula:

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