Source reagent composition and method for chemical vapor deposition formation of Zr/Hf silicate gate dielectric thin films

Source reactant composition and method for chemical vapor deposition forming of zirconium silicate/hafnium silicate gate dielectric film

Background of the invention

Field of invention

The present invention relates to a source reactant composition and method for forming a zirconium silicate/hafnium silicate thin film gate dielectric structure for microelectronic devices.

Description of related skills

The formation of stable gate dielectric films is an increasingly important focus of the research and development of microelectronic devices.

Zirconium Silicate (ZrSiO₄) And hafnium silicate (HfSiO₄) Is a potentially useful material for these gate dielectric films on silicon substrates. The source reagents and methods used to form such gate dielectric films are extremely important for providing gate structures with satisfactory characteristics in production devices. Specifically, the source reactant and method must be able to form a gate dielectric film on a clean silicon surface without the main generation of silicon dioxide (SiO₂), local doped SiO₂And/or other side reactions of impurity on the surface that will reduce the dielectric constant and impair the performance of the product microelectronic device.

Summary of the invention

One aspect of the present invention relates to a precursor composition for forming a metal silicate thin film dielectric on a substrate, and the precursor composition includes a source reactant selected from the following components:

(a) A single-source precursor for forming a zirconium silicate film, wherein the precursor is a compound or coordination complex containing Zr, O and Si as its constituents;

(b) A single-source precursor used to form a hafnium silicate film, wherein the precursor is a compound or coordination complex containing Hf, O, and Si as its constituents;

(c) Precursor mixture, including (1) containing silicon alkoxide coordinated to metal M (Silica oxide) the first precursor metal compound or complex of the ligand, where M=Zr or Hf, and (2) the second precursor containing the aliphatic alkoxide ligand coordinated to the metal M Metal compounds or complexes, where M=Zr or Hf, where the relative ratio of the first and second precursors to each other is used to control the establishment of the desired M/Si ratio in the deposited silicate film;

(d) Precursor mixture, including (1) a first precursor metal compound or complex containing metal M, where M=Zr or Hf, and (2) a second precursor silicon compound that does not contain this metal M Or complex, in which the relative ratio of the first and second precursors to each other is used to control the establishment of the desired M in the deposited silicate film_x/Si₁_-_xRatio, where x is from about 0.01 to 0.99;

(e) Precursor mixture, including (1) a first precursor metal compound or complex compound containing metal M, where M=Zr or Hf, and (2) a second precursor silicon compound containing this metal M Or complex, in which the relative ratio of the first and second precursors to each other is used to control the establishment of the desired M in the deposited silicate film_x/Si₁_-_xRatio, where x is from about 0.01 to 0.99;

(f) Precursor metal compounds or complexes, including metal M, where M=Zr or Hf, at least one alkoxide ligand and at least one β-diketone ligand, such precursor metal compounds or If necessary, the complex contains silicon;

(g) Precursor metal compound or complex (d), wherein the second precursor silicon compound or complex not containing this metal M is a gas under STP, for example, silane, and the first and second The relative ratio of the two precursors to each other is controlled to establish the desired M in the deposited silicate film._x/Si₁_-_xRatio, where x is from about 0.01 to 0.99;

(h) Precursor metal compounds or complexes, including metal M, where M=Zr or Hf, at least one alkoxide ligand and at least one β-diketone ligand, and such precursor metal compounds or complexes may further contain silicon as required;

(i) Precursor metal compound or complex containing no silicon (e), combined with a second silicon-containing precursor compound or complex;

(j) A precursor metal compound or complex containing silicon (e) is combined with a second precursor metal compound or complex containing metal M that does not contain silicon, where M=Zr or Hf; and

(k) Compatible mixtures of any two or more of the aforementioned categories (a)-(i).

The precursor composition may further include a solvent medium, for example, selected from ethers, ethylene glycol dimethyl ether, tetraglyme, amines, polyamines, alcohols, glycols, aliphatic hydrocarbon solvents, and aromatic hydrocarbons. Solvents, solvents of cyclic ethers (for example, tetrahydrofuran, etc.), and compatible combinations of two or more of the foregoing solvents.

Another aspect of the present invention relates to a method for forming a metal silicate gate dielectric film on a substrate, which includes evaporating a precursor composition to form a precursor vapor, and causing the precursor vapor to interact with the substrate at a high temperature Contact to deposit a metal silicate gate dielectric film on the substrate, wherein the precursor composition includes a source reactant selected from the following components:

(a) A single-source precursor for forming a zirconium silicate film, wherein the precursor is a compound or coordination complex containing Zr, O and Si as its constituents;

(b) A single-source precursor used to form a hafnium silicate film, wherein the precursor is a compound or coordination complex containing Hf, O, and Si as its constituents;

(c) Precursor mixture, including (1) a first precursor metal compound or complex containing a silicon alkoxide (silicon oxide) ligand coordinated to metal M, where M=Zr or Hf, and ( 2) Contains aliphatic alkoxide ligands coordinated to metal M The second precursor metal compound or complex, where M=Zr or Hf, where the relative ratio of the first and second precursors to each other is used to control the establishment of the desired M/Si in the deposited silicate film Compare;

(d) Precursor mixture, including (1) a first precursor metal compound or complex containing metal M, where M=Zr or Hf, and (2) a second precursor silicon compound that does not contain this metal M Or a complex, in which the relative ratio of the first and second precursors to each other is used to control the establishment of the desired M/Si ratio in the deposited silicate film;

(e) Precursor mixture, including (1) a first precursor metal compound or complex compound containing metal M, where M=Zr or Hf, and (2) a second precursor silicon compound containing this metal M Or a complex, in which the relative ratio of the first and second precursors to each other is used to control the establishment of the desired M/Si ratio in the deposited silicate film;

(f) Precursor metal compounds or complexes, including metal M, where M=Zr or Hf, at least one alkoxide ligand and at least one β-diketone ligand, such precursor metal compounds or If necessary, the complex contains silicon;

(g) Precursor metal compound or complex (d), wherein the second precursor silicon compound or complex not containing this metal M is a gas under STP, for example, silane, and the first and second The relative ratio of the two precursors to each other is controlled to establish the desired M in the deposited silicate film._x/Si₁_-_xRatio, where x is from about 0.01 to 0.99;

(h) A precursor metal compound or complex containing no silicon (e), combined with a second precursor compound or complex containing silicon;

(i) Precursor metal compounds or complexes containing silicon (e), and those containing gold The second type of precursor metal compound or complex combination that does not contain silicon, where M=Zr or Hf; and

(j) A compatible mixture of any two or more of the aforementioned categories (a)-(i). The term "film" as used herein refers to a layer of material with a thickness of less than about 100 microns.

Other aspects, features, and specific examples of the present invention will be more apparent from the subsequent disclosure and the scope of the attached patent application.

Detailed description of the invention and its preferred specific examples

The following U.S. patents and patent applications are incorporated into this text as reference materials:

. U.S. Patent Application No. 08/835,768 filed in the name of Thomas H. Baum et al. on April 8, 1997;

. U.S. Patent Application No. 08/484,654 filed in the name of Robin A. Gardiner et al. on June 7, 1995;

. U.S. Patent Application No. 08/414,504 filed in the name of Robin A. Gardiner et al. on March 31, 1995;

. U.S. Application No. 08/280,143 filed in the name of Peter S. Kirlin and others on July 25, 1994;

. U.S. Patent Application No. 07/927,134 filed in the same name on August 7, 1992;

. An application was filed in the name of Peter S. Kirlin et al. on December 13, 1991, and is now issued as US Patent No. 5,204,314 of US Patent Application No. 07/807,807;

. Application was filed in the name of Peter S. Kirlin and others on January 15, 1994 Please, and issue a certificate as the US Application No. 08/181,800 of US Patent 5,453,494;

. An application was filed in the name of Peter S. Kirlin and others on July 22, 1992, and was issued on January 18, 1994 as US Patent No. 07/918,141 of US Patent 5,280,012;

. U.S. Application No. 07/615,303 filed on November 19, 1990;

. An application was filed in the name of Peter S. Kirlin et al. on September 12, 1990, and was issued on July 6, 1993 as U.S. Patent No. 07/581,631 of U.S. Patent No. 5,225,561;

. U.S. Patent Application No. 07/549,389 filed in the name of Peter S. Kirlin and others on July 6, 1990;

The above-mentioned applications and patents describe the source reactant composition and its synthesis and formulation in different ways, as well as the CVD technology including liquid transport CVD, and provide background and auxiliary information about the implementation of the present invention.

The present invention relates to a source reactant composition and method for forming zirconium silicate and/or hafnium silicate gate dielectric films for semiconductor manufacturing.

The source reactant composition of the present invention can be formulated in different ways, as described more fully below, and it includes the following ingredients:

(a) A single-source precursor for forming a zirconium silicate film, wherein the precursor is a compound or coordination complex containing Zr, O and Si as its constituents;

(b) A single-source precursor used to form a hafnium silicate film, wherein the precursor is a compound or coordination complex containing Hf, O, and Si as its constituents;

(c) Precursor mixture, including (1) containing silicon alkoxide coordinated to metal M (Silica oxide) the first precursor metal compound or complex of the ligand, where M=Zr or Hf, and (2) the second precursor containing the aliphatic alkoxide ligand coordinated to the metal M Metal compounds or complexes, where M=Zr or Hf, where the relative ratio of the first and second precursors to each other is used to control the establishment of the desired M in the deposited silicate film_x/Si₁_-_xRatio, where x is from about 0.01 to 0.99;

(d) Precursor mixture, including (1) a first precursor metal compound or complex containing metal M, where M=Zr or Hf, and (2) a second precursor silicon compound that does not contain this metal M Or complex, in which the relative ratio of the first and second precursors to each other is used to control the establishment of the desired M in the deposited silicate film_x/Si₁_-_xRatio, where x is from about 0.01 to 0.99;

(e) Precursor mixture, including (1) a first precursor metal compound or complex compound containing metal M, where M=Zr or Hf, and (2) a second precursor silicon compound containing this metal M Or complex, in which the relative ratio of the first and second precursors to each other is used to control the establishment of the desired M in the deposited silicate film_x/Si₁_-_xRatio, where x is from about 0.01 to 0.99;

(f) Precursor metal compounds or complexes, including metal M, where M=Zr or Hf, at least one alkoxide ligand and at least one β-diketone ligand, such precursor metal compounds or If necessary, the complex contains silicon;

(g) Precursor metal compound or complex (d), wherein the second precursor silicon compound or complex not containing this metal M is a gas under STP, for example, silane, and the first and second The relative ratio of the two precursors to each other is controlled to establish the desired M in the deposited silicate film._x/Si₁_-_xRatio, where x is from about 0.01 to 0.99;

(h) A precursor metal compound or complex containing no silicon (e), combined with a second precursor compound or complex containing silicon;

(i) A precursor metal compound or complex containing silicon (e) is combined with a second precursor metal compound or complex containing metal M that does not contain silicon, where M=Zr or Hf; and

(j) A compatible mixture of any two or more of the aforementioned categories (a)-(i). The precursor formula of the present invention can be used in the addition form suggested by the following chemical formula:

M(OR)₂(β-diketone)₂L_y;

[M=O(β-diketone)₂L_y]₂and

M(OR)₄L_y

Among them, each R system is selected from including C₁-C₈Alkyl and its alkyl substituents are each selected from the group including C₁-C₈The trialkylsilyl group of the alkyl group; L is a Lewis base ligand, and y is from about 1/2 to 8.

Alternatively, the precursor formula of the present invention can be represented by the following chemical formula:

M(OR-L)₄

Among them, each R system is selected from including C₁-C₈Alkyl and its alkyl substituents are each selected from the group including C₁-C₈The trialkylsilyl group of the alkyl group, and L may be Lewis base included in the ligand species that can be bonded to the metal center.

The precursor formulation of the present invention can be used in liquid transport CVD, and the related metal (Zr and/or Hf) silicate film can be formed on the substrate or microelectronic device precursor structure as the gate dielectric on it Floor.

In liquid transport CVD, for example, the source reactant compound or complex can be quickly heated and evaporated at ambient temperature (for example, room temperature, 25°C) or other source reactants. When the precursor vapor for the CVD process is formed into a liquid phase at the supply temperature, the source liquid may include the compound or the complex itself. Alternatively, if the source reactant compound or complex is solid at the ambient or supply temperature, the compound or complex can be dissolved or suspended in a compatible solvent medium compatible with it to provide acceptable rapidity. Heating and evaporation form the liquid phase composition of the precursor vapor for the CVD process. Then the precursor vapor generated by the evaporation is combined with the delivery gas (for example, He, Ar, H₂, O₂Etc.) are combined and transported to the chemical vapor deposition reactor, where the vapor is brought into contact with the substrate at high temperature, and the material is deposited from the vapor phase on the substrate or the precursor structure of the semiconductor device set in the CVD reactor .

The preferred metal alkoxide compounds of the present invention include compounds with the following chemical formula:

M(OR)₄，

Where M is Zr or Hf;

Each R series is selected from including C₁-C₈Alkyl and its alkyl substituents are each selected from the group including C₁-C₈The trialkylsilyl group of the alkyl group.

Particularly preferred metal alkoxide β-diketone compounds of the present invention include compounds with the following chemical formula:

<chemistry general="n"><img file="TW570997B_D0001.tif" /></chemistry>

<chemistry general="n"><img file="TW570997B_D0002.tif" /></chemistry>

Among them: M is Zr or Hf;

Each R series is selected from including C₁-C₈Alkyl and its alkyl substituents are each selected from the group including C₁-C₈The trialkylsilyl group of the alkyl group; and each R'is selected from the group including C₁-C₈Alkyl and C₁-C₈Haloalkyl.

Therefore, the β-diketone group of the above metal precursor may include, for example, 2,4-pentanedione acac; 1,1,1-trifluoro-2,4-pentanedione tfac; 1,1,1 ,5,5,5-hexafluoro-2,4-pentanedione hfac; 2,2,6,6-tetramethyl-3,5-heptanedione thd; 2,2,7-trimethyl -3,5-octanedione tod; 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione fod; etc.

One particularly preferred metal precursor of the above types has each R=tertiary butyl group or trialkylsilyl group, for example, trimethylsilyl group and each R=tertiary butyl group.

Mixed alkoxide β-diketone complexes with or without silicon component of Zr and/or Hf can be used. Examples of this type of silicon-containing complexes include Zr (OSiMe₃)₂(thd)₂, Zr (OSiMe₃)₄, Hf(OSiMe₃)₄, Hf(OSiMe₃)₂(thd)₂; Due to the expected zirconium silicate film and/or hafnium silicate The metal, silicon and oxygen components are derived from these single precursor species, so these complexes are single-source precursors.

If such mixed alkoxide β-diketone complexes do not contain silicon, they can be appropriately combined with silicon precursors to produce the product metal silicate film. If such mixed alkoxide β-diketone complexes contain silicon, they can be appropriately combined with silicon-free Zr and/or Hf precursors to provide the desired metal/silicon in the product dielectric film Compare. For example, aliphatic alkoxides of hafnium, such as Hf(OiPr)₂(thd)₂, Used in combination with a second Si-containing precursor, such as a precursor containing silicon alkoxide (silicon oxide), to deposit HfSiO₄Membrane. The film.

By using a precursor composition including two or more source reactant compounds or complexes, one of the precursors includes at least part of the metal to be added to the product dielectric metal silicate film, and the other precursor includes At least part of the silicon to be added to the product dielectric metal silicate film can be selected by selecting the ratio of these respective precursors to change the stoichiometric composition of the metal silicate dielectric film (metal/silicon Ratio), and obtain the desired characteristics of structure and performance electrical properties in the product film. For example, a metal-free silicon source reactant can be used in combination with a silicon-free metal source reactant to control the ratio of Zr/Si or Hf/Si film.

Alternatively, the first metal and silicon-containing precursor can be used in combination with a metal-containing/silicon-free precursor or a metal-free/silicon-containing precursor to obtain the desired film characteristics and film stoichiometry.

As mentioned above, the first metal- and silicon-containing precursor can be used in combination with a precursor that does not contain this metal, and the metal-free precursor can be Gas, such as silane. This precursor can be used in an oxidizing environment such as O₂Or N₂The combination of O results in the desired film properties and film stoichiometry.

To give a clear example, Zr (OSiMe₃)₄And Zr(O-tBu)₄It is better to mix in a gas stream, such as a delivery gas, or in a single "cocktail" solution in a solvent such as octane, and to deposit ZrSiO₄Appropriate stoichiometry is produced in the film. Hf(OSiMe₃)₄And Hf(O-tBu)₄Mixed in the gas phase, or better in a single "cocktail" solution, used to deposit the desired stoichiometric HfSiO₄film.

Other compatible aliphatic alkoxides can also be used, and equivalent results can be obtained in these applications.

The films produced in the broad practice of the present invention include stoichiometric metal silicate films and films that deviate from stoichiometry (insufficient metal). In the case where the precursor composition includes different source reactants that provide different metal and/or silicon content, the respective source reactants can be supplied with different compositions to obtain the relevant product metal silicate film Desired stoichiometric characteristics. In this way, the electrical properties, including dielectric constant and leakage, can be controlled and tightly adjusted to desired applications, such as gate dielectric films in integrated circuits.

The most important example of the film stoichiometry of the present invention is Zr for zirconium silicate_.₂₀/Si_.₈₀, And Hf for hafnium silicate_.₀₅/Si_.₉₅。

In the use of two different precursors, one of which contains silicon and the second contains Zr/Hf, while depositing ZrSiO₄And HfSiO₄When filming, compatible chemistry is required, so that the individual precursors can be mixed with each other and achieve a reproducible film growth process without adverse effects such as solution degradation and particle formation.

For example, Zr(O-tBu) can be used₄With Si (O-tBu)₄Combine to form stoichiometric ZrSiO₄The film is a gate dielectric material. The two precursors can be mixed in an organic solvent, a single solution such as a "cocktail", or they can be introduced from two separate storage tanks and mixed in the gas flow to the CVD reactor. Other alkoxides of Zr/Hf and Si can be used in a similar manner, and the same results can be obtained. The limitation is that the respective alkoxides will not produce undesired and undesirable (undesired) new precursor species. Non-degenerate ligand exchange. Therefore, use the same alkoxide ligand type for each metal and silicon precursor used in combination with each other, for example, methoxide, ethoxide, isopropoxide, tertiary butoxide, trialkyl silicon oxide Things and so on are better.

However, techniques such as pulsed CVD can be used to use separate metal and silicon precursors, for example, alkoxide precursors, regardless of the ligand body and the ligand exchange mechanism, in which incompatible precursors will be used. It is temporarily separated in the introduction line to limit particle formation and undesired ligand exchange reactions (chemical reactions).

The metal silicate film can be formed by a mixture of metal alkoxide β-diketones in the broad practice of the present invention, in which one metal alkoxide β-diketone precursor contains silicon, and the second metal alkoxide β -The diketone precursor does not contain silicon.

For example, Zr (OSiMe₃)₂(thd)₂The mixture of silicon-free precursors such as Zr (alkoxide)₂(thd)₂, Zr(thd)₄, Or [O=Zr(thd)₂]₂Used in combination to deposit zirconium silicate films, in which the stoichiometry of the film is controlled by the relative ratio of the two precursor types. A wide range of thin films can be deposited in this way Composition. A relative hafnium precursor method can be used to form a hafnium silicate film.

Figure 1 shows the Zr(O-SiMe₃)₂(thd)₂And Zr(thd)₄The comparison TGA (thermal weight loss) graph. Zr(OSiMe₃)₂(thd)₂TGA trace and Zr(thd)₄The TGA trace shows that these co-reactants have the ability to control ZrSiO₄The beneficial nature of its growth.

The definite and illustrative zirconium precursors of the present invention include compounds of the following chemical formula:

<chemistry general="n"><img file="TW570997B_D0003.tif" /></chemistry>

The complex compound of formula I-Zr(OR)₂(β-diketone)₂In this, R may be a tertiary butyl group or a trimethylsilyl group, and Rmay be a tertiary butyl group, for example. The β-diketone in the complex of formula I may be thd, for example. The precursor may include a mixture of complexes of formula I, including a first precursor of the type where R is a tertiary butyl group and a second precursor of the type where R is a trimethylsilyl group. The formula II shows the related oxy-linked (-O-) dimer, which can be used in combination with the complex compound of formula I in which R is a trimethylsilyl group, for example, to provide a source reactant for forming a zirconium silicate film The precursor cocktail. The oxy-linked (-O-) dimer can be, for example, oxyzirconium bis(thd) dimer, [O=Zr(thd)₂]₂。

Therefore, when the molecular structure of double alkoxide of I and Zr (OSiMe₃)₂(β-diketone)₂When the precursor is used in combination in a common solvent medium, it can be used for "Adjustment" to limit the ligand exchange reaction; alternatively, liquid transport technology can be used to transport the bis-alkoxide precursor in a separate solution. The zirconium "oxy" bis(diketone) dimer of the chemical formula II can also be used as the source of Zr without introducing the Si content into the deposited film.

Related considerations can be applied to the following similar hafnium source reactants:

<chemistry general="n"><img file="TW570997B_D0004.tif" /></chemistry>

In the previous hafnium source reactants of chemical formulas III and IV, the alkoxy substituent R in chemical formula III can be methyl, ethyl, isopropyl, n-butyl or trimethylsilyl, and in chemical formulas III and IV The substituent R'in the β-diketone group can be alkyl, halo, haloalkyl (for example, perfluoroalkyl), etc., wherein the alkyl substituent can be methyl, ethyl, iso Propyl, n-butyl, tertiary butyl, etc.

The source reactant of the present invention can be used in a liquid precursor composition containing any suitable solvent medium compatible with the source reactant used to form a specific dielectric film. Illustrative examples of solvent media that can be used effectively in different ways are ether, ethylene glycol dimethyl ether, tetraglyme, amine, polyamine, alcohol, glycol, aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent, cyclic A compatible combination of two or more ethers and the aforementioned solvents.

The precursor liquid can be evaporated by any suitable evaporation device in any suitable manner to form the relevant precursor vapor for contact with the high temperature substrate on which the metal silicate dielectric film is to be formed. Evaporation can be performed, for example, by using a liquid delivery evaporator unit of the type that is commercially available from Advanced Technology Materials, Inc. (Danbury, CT) under the registered trademark VAPORSOURCE, in which the precursor liquid is discharged to the heating evaporation element, Such as porous sintered metal surface, and quickly evaporate. The evaporator can be set to accept delivery gases such as argon, helium, etc., and oxygen-containing gas can be introduced as needed to form a metal silicate film. Therefore, the precursor vapor flows to the chemical vapor deposition chamber and contacts the substrate on which the dielectric film is to be deposited. In the deposition operation, heating devices such as a radiant heating combination, a crystal seat containing a resistance heating element, a microwave heat generator, etc., are used to maintain the substrate at an appropriate high temperature. The proper method conditions of the temperature, pressure, flow rate and concentration (partial pressure) of the metal and silicon components are maintained for a sufficient time to form the desired film thickness, for example, in the range of thickness from about 2 nanometers to about 500 microns, And a dielectric film with appropriate dielectric film characteristics.

Figures 2-5 show the thermal characteristics of illustrative source reactants useful in practicing the present invention. Figure 2 Si (O-SiMe₃)₄STA diagram in argon. Figure 3 Zr (O-SiMe₃)₂(thd)₂STA diagram in argon. Figure 4 Series Si (O-SiMe₃)₄STA diagram and Zr(O-SiMe₃)₂(thd)₂STA diagram in argon. Figure 5 Series Zr (O-SiEt₃)₄STA diagram in argon.

The characteristics, aspects and advantages of the present invention are further demonstrated with reference to the following non-limiting embodiments of the present invention.

Example 1

Zr(thd)

2

(O-SiMe

3

)

2

Synthesis

Use standard Schlenk and dry box technology, with nitrogen as the inert gas.

a) Zr(thd)₂Cl₂. Add two-fold excess (four equivalents) of 2,2,6,6-tetramethyl-3,5-heptanedione (Hthd) dropwise to ZrCl₄Reflux suspension in ether. The solid was gradually dissolved and refluxing was continued for 16 hours. Allow the solution to cool to room temperature and concentrate until Zr(thd)₂Cl₂Start to settle. The precipitate was redissolved in a minimum amount of ether; the solution was filtered and placed in a freezer (-20°C) for 40 hours. The resulting white precipitate was filtered and dried under nitrogen. Yield: 75-90%.

b) Zr(thd)₂(OSiMe₃)₂. Zr(thd) to make 1 to 2 mol ratio₂Cl₂And LissiMe₃Suspended in pentane, and stirred the mixture for 16 hours. When the LiCl is separated by filtration, the slightly yellow solution is evaporated to dryness to obtain Zr(thd) with a yield of about 65%₂(OSiMe₃)₂。

Example 2

Zr(O-SiEt

3

)

4

Synthesis

Using standard Schurnke technology, nitrogen is used as an inert gas. 10% excess HOSiEt dissolved in benzene₃(4.1 equivalents) at a rate approximately equal to the distillation rate of the benzene/isopropanol azeotrope from the reaction flask, added dropwise to Zr(0ⁱPr)₄Dissolved in the refluxing solution of benzene. After the addition is complete, continue to reflux until all benzene is distilled off. The excess silanol is removed in a vacuum of 0.2 torr at a temperature below 100°C. Then the temperature was increased, and the clear liquid product was steamed at 147°C/0.1 Torr Distilled. Yield: 82%.

Example 3

The organic solution (octane) containing bis(trimethylsilyl oxide) bis(2,2,7,7-tetramethyl-3,5-heptanedione) zirconium is transported to the heating evaporation zone by liquid transportation, And transported to the CVD reactor. The vapor stream is reacted on a substrate heated to a high temperature (300-700°C) in an oxidizing environment to deposit a zirconium silicate gate dielectric film. Through the use of specific CVD method conditions or through the co-addition of a second silicon-free Zr source [ie four (2,2,7,7-tetramethyl-3,5-heptanedione) zirconium, bis(alkyloxy) Compound) bis(2,2,7,7-tetramethyl-3,5-heptanedione) zirconium or (oxy 2,2,7,7-tetramethyl-3,5-heptanedione) two Polymer zirconium] to increase the Zr content in the deposited film, or use non-zirconium-free Si (alkoxy) silicon to increase the Si content in the deposited film and control the Zr/Si ratio.

Example 4

The organic solution (octane) containing bis(trimethylsilyl oxide) bis(2,2,7,7-tetramethyl-3,5-heptanedione)hafnium is transported to the heating evaporation zone by liquid transportation, And transported to the CVD reactor. The vapor stream is reacted on a substrate heated to a high temperature (300-700°C) in an oxidizing environment to deposit a hafnium silicate gate dielectric film. Through the use of specific CVD method conditions or through the co-addition of a second non-silicon-free Hf source (ie Si (2,2,7,7-tetramethyl-3,5-heptanedione) hafnium, bis(alkoxy) Bis(2,2,7,7-tetramethyl-3,5-heptanedione) hafnium or hafnium alkoxide precursor] to increase the Hf content in the deposited film, or use non-hafnium (Alkoxide) silicon to increase the Si content in the deposited film and control the Hf/Si ratio.

Example 5

The pure liquid containing zirconium (triethyl silicon oxide) is transported to the heating evaporation zone by liquid transport, and transported to the CVD reactor. The vapor stream is reacted on a substrate heated to a high temperature (300-700°C) in an oxidizing environment to deposit a zirconium silicate gate dielectric film. Through the use of specific CVD method conditions (temperature, pressure, flow, etc.), or through the co-addition of a second non-silicon-free liquid Zr source [ie 4 (2,2,7,7-tetramethyl-3,5 -Heptanedione) zirconium, bis(alkoxide) bis(2,2,7,7-tetramethyl-3,5-heptanedione) zirconium or 4 (tertiary butoxide) zirconium] to improve deposition The Zr content in the film, or the use of silicon species that do not contain zirconium, such as Si (ethoxylated) silicon, can increase the Si content in the deposited film and control the Zr/Si ratio.

Example 6

The pure liquid containing hafnium (triethylsilica) is transported to the heating evaporation zone by liquid transport, and transported to the CVD reactor. The vapor stream is reacted on a substrate heated to a high temperature (300-700°C) in an oxidizing environment to deposit a hafnium silicate gate dielectric film. Through the use of specific CVD method conditions (temperature, pressure, flow, etc.), or through the co-addition of a second non-silicon-free liquid Hf source [ie 4 (2,2,7,7-tetramethyl-3,5) -Heptanedione) hafnium, bis(alkoxide) bis(2,2,7,7-tetramethyl-3,5-heptanedione) hafnium or Si (tertiary butoxide) hafnium] to improve deposition The Hf content in the film, or the use of silicon species that do not contain hafnium, such as Si (ethoxylated) silicon, can increase the Si content in the deposited film and control the Hf/Si ratio.

Example 7

The pure liquid containing zirconium (trialkylsiloxy) zirconium is transported to the heating evaporation zone by liquid transport, and transported to the CVD reactor. Oxidize the vapor stream In the environment, it reacts on a substrate heated to a high temperature (300-700°C) to deposit a zirconium silicate gate dielectric film. The Zr/Si ratio is controlled by using specific CVD method conditions (temperature, pressure, flow rate, etc.) to deposit a thin film exhibiting a stoichiometric ratio similar to the atomic ratio of the element in the precursor source. Therefore, non-stoichiometric zirconium silicate can be deposited directly from a single source precursor. The stoichiometry of the deposited film can be changed by co-adding a second non-silicon-free liquid Zr source to increase the Zr content in the deposited film, or by using a silicon species without zirconium to increase the Si content in the deposited film.

Example 8

The pure liquid containing hafnium (trialkylsilica) is transported to the heating evaporation zone by liquid transport, and transported to the CVD reactor. The vapor stream is reacted on a substrate heated to a high temperature (300-700°C) in an oxidizing environment to deposit a hafnium silicate gate dielectric film. The Hf/Si ratio is controlled by using specific CVD process conditions (temperature, pressure, flow rate, etc.) to deposit a thin film that exhibits a stoichiometric ratio similar to the atomic ratio of the elements in the precursor source. Therefore, non-stoichiometric hafnium silicate can be deposited directly from a single source precursor. The stoichiometry of the deposited film can be changed by co-adding a second liquid Hf source without silicon to increase the Hf content in the deposited film, or by using a silicon species without hafnium to increase the Si content in the deposited film.

Although the present invention has been disclosed in the text in different ways with reference to specific examples and features, it should be understood that the specific examples and features described in the foregoing are not meant to limit the present invention, and those skilled in the art should be aware of other changes, modifications, and others. Specific examples. Therefore, the present invention should be interpreted broadly in accordance with the scope of the patent application described later.

Figure 1 is the Zr(O-SiMe₃)₂(thd)₂And Zr(thd)₄The comparison TGA chart.

Figure 2 Si (O-SiMe₃)₄The STA diagram.

Figure 3 Zr (O-SiMe₃)₂(thd)₂The STA diagram.

Figure 4 Series Si (O-SiMe₃)₄And Zr(O-SiMe₃)₂(thd)₂The STA diagram.

Figure 5 Series Zr (O-SiEt₃)₄STA diagram of a single source precursor.