KR101546319B1 - Tungsten precursors and the method for depositing tungsten-containg films - Google Patents

Abstract

The present invention provides a method for depositing a tungsten-containing film. The method for depositing a tungsten-containing film on a substrate comprises the steps of: introducing a tungsten precursor compound into a reactor in which at least one substrate is arranged inside; and depositing at least some of the tungsten precursor compound on at least one substrate and forming a tungsten-containing film. In addition, the method relates to a tungsten precursor composition capable of ensuring thermal stability and obtaining the tungsten-containing film under mild conditions at a high yield.

Description

TECHNICAL FIELD The present invention relates to a tungsten precursor for depositing a tungsten-containing film and a tungsten-containing film containing the tungsten precursor,

The present invention relates to an organic-tungsten precursor suitable for use in chemical or atomic layer deposition, which is a deposition process that can be used to form dielectric films in semiconductor devices as organometallics, and a method of making film deposition using the same.

Chemical vapor deposition (CVD) and atomic layer deposition (ALD) can be used to deposit thin films for semiconductor devices, such as metal, oxide, nitride, etc., because they can achieve conformal films Has been applied as a technique for deposition. Since film growth is mainly controlled by the chemical reaction of metal-organic compounds (precursors), it is important to develop optimal precursors by predicting their nature and reaction process. Thus, efficient precursors have been developed to obtain specific properties for certain types of films.

Precursors are molecules for CVD and ALD processes and some of their unique properties must be considered before using them. First, liquid form and / or sufficient vapor pressure is required to facilitate transport of the gaseous precursor from the containing vessel into the reaction chamber. Second, long-term thermal stability is required under the storage conditions and transportation conditions, and gas phase thermal stability is also necessary to prevent impurities from entering the film. Strong reactivity to a reactive gas such as ammonia or oxygen is required in order to easily convert the third precursor into the required film on the sample substrate. Another important requirement to be considered for the precursor in the precursor design phase is to remove impurities from the film from the ligand during the deposition process.

Tungsten is used in a variety of applications that are useful for making nano-devices. Deposition of pure tungsten may be used to fill the holes ("contact holes") that make the junctions to the transistor source and drain, or to fill the vias between successive layers of metal. This approach is known as the "tungsten plug" process. With WF ₆ , the use of tungsten can be diversified because of the good properties of the deposited film. However, it is necessary to provide an adhesion / barrier layer, for example Ti / TiN, in order to protect the underlying Si by infiltration with fluorine, or to ensure the adhesion of tungsten to silicon dioxide.

Tungsten-silicide may be used to increase the conductivity of the gate line on top of the polysilicon gate and thus increase the transistor speed. This method is widely used in DRAM fabrication. The gate at this time is a word line for the circuit. Although WF ₆ and SiH ₄ can be used, dichlorosilane (SiCl ₂ H ₂ ) is more commonly used as a silicon source, because it allows higher deposition temperatures and results in lower fluorine concentrations in the deposited films .

Tungsten nitride (WNx) is considered a good barrier to copper diffusion in microelectronic circuits. WNx can also be used for electrodes for thin-film capacitors and field-effect transistors.

WF ₆ can be used for the deposition of pure tungsten films in CVD mode using H ₂ at high temperatures because of the +6 oxidation state of liquid and highly volatile W (Applied Surface Science, 73, 1993, 51-57 ; AppliedSurface Science, 78, 2, 1994, 123-132). WF ₆ can also be used in CVD mode in combination with silane for the production of tungsten silicide films at low temperatures (Y. Yamamoto et al. Proc. Int. Conf. On CVD-XIII (1996) 814; Surface Science 408 (1998) 190-194). However, WF ₆ is limited by the high thermal budget required for the deposition of pure tungsten film or due to fluorine which causes etching of the underlying silicon surface.

Can be used to deposit pure tungsten or tungsten nitride films in CVD mode because of the zero oxidation state of W in W (CO) ₆ . However, due to the high toxicity of this material, it has been limited to mass production (Kaplan et al J. Electrochem. Soc. 1979, 117, 693; Sun et al., Solid Films 2001, 397, 109).

W (CO) ₂ (1,3-butadiene) ₂ can be used in the CVD mode, but deposition of tungsten carbide film is formed (Jipa et al Chemical Vapor Deposition 2010, 16 (7-9), 239).

However, the +6-oxidation state of W in the biscyclopentadienyl tungsten precursor having the formula W (RCp) ₂ H ₂ can be used in a CVD mode for the deposition of pure tungsten, but a high deposition temperature is required, resulting in carbon contamination (Zinn et al. Adv. Mater. 1992, 375; Spee et al., Sci. Eng 1993 (B17) 108; Ogura et al J.of Vac. Sci. Tech. 2008, 26, 561).

US 7,560,581 B2 discloses the use of bis-alkylimidobis-dialkylamino tungsten precursors for the production of tungsten nitride in ALD mode with or without copper barrier diffusion applications.

Several diazabutadiene molecules have been developed apart from the tungsten precursor mentioned above. Diazabutadiene (DAD) ligands are diimine ligands that can be used under different oxidation states.

U.S. Patent No. 7,754,908 to Reuter et al. Discloses the use of bis-alkylimidodiazabutadiene tungsten precursors for the production of tungsten-containing films. However, the use of an alkyl imido is disadvantageous in that carbon can be introduced into the resulting film. The tungsten molecule may contain several kinds of ligands other than homologous ligands. Thus, their synthesis takes place in several stages, resulting in complexity and difficulty of synthesis, which ultimately leads to higher costs.

WO 0212/027357 to Winter discloses a method of forming a thin film on a substrate comprising contacting the surface with a precursor compound having a transition metal and at least one alkyl-1,3-diazabutadiene ligand .

The deposition of a tungsten-containing film (pure tungsten, tungsten nitride, or tungsten silicide) in the CVD or ALD mode can be problematic due to high C, O, or F content in the film. Therefore, a tungsten-containing precursor suitable for CVD or ALD deposition processes is needed. Preferred properties of tungsten-containing precursors for these applications are: i) liquid form or low melting point solids; ii) high volatility; iii) thermal stability to avoid degradation during handling and transportation; And iv) suitable reactivity during the CVD / ALD process; And v) a pure tungsten film must be deposited in CVD or ALD (thermal or plasma mode) at a temperature of less than 200, preferably less than 150, and at the same time thermal stability should not be too high to permit deposition at low temperatures.

KR 1020120059440 A KR 1020080093393 A KR 1020110044724 A US 7560581 B2

It is an object of the present invention to provide a novel tungsten precursor compound as a precursor for depositing a tungsten thin film under chemical vapor deposition or atomic layer deposition process conditions, and to provide a tungsten deposition method using the same.

The present invention provides a tungsten (W) precursor compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1, X, Y are _{^{O, NR 1, NR 1 2}} , is selected from the group consisting of CR ^1, Z is ^{-CR 1 -CR 1 C = CR 1} -, = CR 1 -CR 1 -, = _{^{CR 1 -, = CNR 1 2}} -, -CH 2 -CR 1 2 - is selected from the group consisting of, R and R ¹ are each independently H; C ₁ -C ₁₀ linear, branched, or cyclic alkyl groups; C ₁ -C ₁₀ linear, branched, or alkylsilyl groups, cyclic alkylsilyl groups (mono, bis, or trisalkyl); C ₁ -C ₁₀ linear, branched, or cyclic alkylamino group represented by NR ² ₂ , wherein R ² is H or C ₁ -C ₁₀ linear, branched, or cyclic alkyl or C ₆ -C ₁₂ aryl Lt; / RTI > C ₁ -C ₁₀ linear, branched, or cyclic fluoroalkyl groups wherein some or all of the substituents are F; And alkoxy groups substituted with C ₁ -C ₁₀ linear, branched, cyclic alkyl or aryl groups, and n and m are integers of 1 or 2.

According to a specific example of the present invention, a precursor compound in which R is a t-butyl group and m is 2 is coordinated with a ligand in the above formula (1) is preferable, and these compounds are represented by the following formula (2).

(2)

Preferable examples of ligands coordinated in the present invention are ligands represented by the following formulas (3) to (11), and a tungsten-containing film can be deposited with a precursor compound in which a ligand represented by one of these ligands is coordinated.

[Chemical Formula 3]

   [Chemical Formula 7] < EMI ID =

    [Chemical Formula 10] < EMI ID =

In the tungsten compound in which the ligand is coordinated, R ^a , R ^b , R ^c , R ^d , and R ^e are each independently the same as R ¹ defined above. There is also provided a method of depositing a tungsten containing film by implanting at least one of the disclosed tungsten precursor compounds into a reactor in which at least one substrate is disposed and depositing at least a portion of the molecules of the tungsten precursor compound onto the at least one substrate to form a tungsten containing film do. Such deposition methods may also include one or more of the following deposition conditions.

The process may be carried out at a temperature of from about 20 ° C to about 600 ° C, and preferably at a temperature of from about 100 ° C to about 400 ° C. And in another embodiment from about 20 [deg.] C to about 150 < 0 > C. The pressure conditions in the process may be performed at a pressure of from about 0.1 Pa to about 10 ⁵ Pa, and preferably at a pressure of from about 2.5 Pa to about 10 ³ Pa.

The methods provided in the present invention can be used for chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma CVD, plasma ALD, pulse CVD, low pressure CVD, subatmospheric CVD, atmospheric CVD, hot- And supercritical fluid deposition, preferably with thermal atomic layer deposition (ALD).

According to a specific example of the present invention, a tungsten-containing film is made of tungsten (W), tungsten silicide (WSi), tungsten nitride (WN), tungsten carbide (WC), carbon nitride tungsten (WNC) ≪ / RTI >

Further, the method provided in the present invention is characterized in that the reactive gas is introduced into the reactor simultaneously or alternatively with the introduction of the molecules of the tungsten compound, and the reactive gas is a reducing agent. The reducing agent may be selected from the group consisting of N ₂ , H ₂ ; SiH ₄ ; Si ₂ H ₆ ; Si ₃ H ₈ ; NH ₃ ; (CH _{3) 2} SiH _2; (C ₂ H ₅ ) ₂ SiH ₂ ; (CH ₃₎ SiH _3; (C ₂ H ₅ ) SiH ₃ ; Phenylsilane; N ₂ H ₄ ; N (SiH ₃ ) ₃ ; N (CH ₃₎ H _{2; N (C 2 H 5) H} 2; N (CH _{3) 2} H; _{N (C 2 H 5) 2} H; N (CH _{3) 3; N (C 2 H 5) 3} ; (SiMe ₃ ) ₂ NH; (CH ₃₎ HNNH _2; (CH _{3) 2} NNH _2; Phenylhydrazine; B ₂ H ₆ ; 9-borabicyclo [3,3,1] nonane; Dihydrobenzene furan; Pyrazoline; Trimethyl aluminum; Dimethyl zinc; Diethylzinc; Its radical species; And mixtures thereof.

In another embodiment, the oxidizing agent may be introduced as a reaction gas into the process of the present invention. The oxidizing agent is O _2; O ₃ ; H ₂ O; H ₂ O ₂ ; NO; NO ₂ ; Carboxylic acid; Its radical species; And mixtures thereof.

The tungsten precursor compound provided in the present invention is a novel compound which is not disclosed in the prior art, and can be easily synthesized, can increase productivity with a high yield, and can deposit a tungsten-containing film at a low temperature. The method of depositing a tungsten-containing film according to the present invention makes it possible to facilitate deposition of a thin tungsten-containing film if necessary by using the novel precursor compound.

1 shows ¹ H NMR analysis data of (t-BuN =) ₂ W (Me-CO = CH-CMe = Ni-Pr) ₂ .
2 shows ¹³ C NMR analysis data of (t-BuN =) ₂ W (Me-CO = CH-CMe = Ni-Pr) ₂ .
3 is a graph showing the thermal characterization of (t-BuN =) ₂ W (Me-CO = CH-CMe = Ni-Pr) ₂ .
FIG. 4 shows data obtained by measuring the vapor pressure of (t-BuN =) ₂ W (Me-CO = CH-CMe = Ni-Pr) ₂ .

Hereinafter, embodiments of the present invention will be described in detail. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

As used in this specification and the appended claims, the meanings of the following terms, abbreviations, and symbols, unless otherwise stated, are as follows.

As used herein, the term "independently" when used in the context of describing an R group means that the subject R group is not only independently selected for other R groups having the same or different numbers, but also for any additional species of the same R group ≪ / RTI > For example, two or three R ^a groups may be the same as or different from R ^b or R ^c , but need not be the same. Also, unless otherwise stated, the values of the R groups are independent of each other when used in different formulas.

The term "alkyl group" as used herein refers to a saturated functional group containing only carbon and hydrogen atoms. The term "alkyl group ", unless otherwise specified, has a single bond of 1 to 30 carbon atoms and refers to a linear, branched or cyclic alkyl group. Examples of linear alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, and the like, examples of branched alkyl groups include, but are not limited to, t-butyl, and examples of cyclic alkyl groups include, , A cyclopentyl group, a cyclohexyl group, and the like.

The term "aryl group" in the present invention refers to a ligand derived from an aromatic molecule such as phenyl, benzyl, tolyl, o-xylyl,

The abbreviation "Me" in the present invention refers to a methyl group, the abbreviation "Et" refers to an ethyl group, "Pr" refers to an n-propyl group, "i-Pr" refers to an isopropyl group, Refers to butyl (n-butyl), "t-Bu" refers to tert-butyl, "s-Bu" refers to sec-butyl; The abbreviation "Cp" refers to cyclopentadienyl, "THF" refers to tetrahydrofuran, and the abbreviation "DME" refers to dimethoxyethane.

(For example, W is tungsten, N is nitrogen, O is oxygen, C is carbon, Si is silicon, F is fluorine, and so on.) The standard abbreviations of the elements of the Periodic Table of Elements are used herein, It means the same thing.

Alkylmolecular derivative ligands containing nitrogen and oxygen determine the mode of bonding between the central element tungsten (W) and the ligand.

For a clearer understanding, the ligands include the structure shown below.

 [Chemical Formula 3]

   [Chemical Formula 7] < EMI ID =

    [Chemical Formula 10] < EMI ID =

The ligand ^{(R a -CO-CR b =} CO-R c, R a -CO = CR b -CR c = NR d, R a -N = CR b -CR c = CR d -NR e, R a - N = CR ^b -CR ^c -NR ^d , R ^a -N═CR ^b -NR ^c R ^d , R ^a -N═C (-NR ^b R ^c ) -NR ^d R ^e , R ^a -CO-NR ^b (W) precursor compounds wherein R ^c , R ^a -C = CR ^b -CH-R ^c , R ^a R ^b -N-CH 2 -CO-R ^c R ^d are coordinated are provided herein. Wherein ^{R a, R b, R c} , R d and R ^e are each H; C ₁ -C ₁₀ linear, branched, or cyclic alkyl groups; C ₁ -C ₁₀ linear, branched, or alkylsilyl groups, cyclic alkylsilyl groups (mono, bis, or trisalkyl); C ₁ -C ₁₀ linear, branched, or cyclic alkylamino group represented by NR ² ₂ , wherein R ² is H or C ₁ -C ₁₀ linear, branched, or cyclic alkyl or C ₆ -C ₁₂ aryl Lt; / RTI > C ₁ -C ₁₀ linear, branched, or cyclic fluoroalkyl groups wherein some or all of the substituents are F; And alkoxy groups substituted with C ₁ -C ₁₀ linear, branched, cyclic alkyl or aryl groups, and n and m are integers of 1 or 2.

Due to the flexibility of the W-N bond in the film deposition dimension, the ligand-coordinated compound can be used for tungsten, nitride-tungsten, carbon nitrogen-tungsten, tungsten oxide, or any other type of tungsten-containing film. These compounds are capable of depositing tungsten-containing films at lower temperatures due to their appropriate thermal stability. The compound may be deposited at a temperature of less than 200 < 0 > C, preferably less than 150 < 0 > C, in a CVD or ALD (thermal or plasma mode) deposition of pure tungsten film. The compound may be used for the deposition of a film having a controlled thickness and composition at the desired temperature.

A preferred example tungsten (W) containing compound comprises a compound represented as follows: (t-Bu-N = ) 2 W (R a -CO-CR b = CO-R c) 2, (t-Bu- ^{_{N =) 2 W (R a}} -CO = CR b -CR c = NR d) 2, (t-Bu-N =) 2 W (R a -N = CR b -CR c = CR d -NR e) _{2, (t-Bu-N} =) 2 W (R a -N = CR b -CR c -NR d) 2, (t-Bu-N =) 2 W (R a -N = CR b -NR c _{^{R d) 2, (t-}} Bu-N =) 2 W (R a -N = c (-NR b R c) -NR d R e) 2, (t-Bu-N =) 2 W (R a _{^{-CO-NR b R c) 2}} , (t-Bu-N =) 2 W (R a -C = CR b -CH-R c) 2, (t-Bu-N =) 2 W (R a R ^b is ^{-N-CH2-CO-R c} R d) 2. the most preferred tungsten precursor compounds are (t-Bu-N =) 2 W (Me-CO = CH-CMe = Ni-Pr) 2.

A method of forming a tungsten-containing layer on a substrate using a deposition process is also provided. The method can be applied to the fabrication of semiconductors, photovoltaic cells, LCD-TFTs, or flat panel type devices. The tungsten-containing film may be produced by depositing one or more of the tungsten precursor compounds described above into a reactor in which one or more substrates are disposed. A variety of known deposition methods can be used to deposit the tungsten-containing film with the tungsten compounds described above. Examples of suitable deposition methods include, but are not limited to, conventional chemical vapor deposition (CVD) or atomic layer deposition (ALD), or other methods of vapor deposition using techniques such as plasma [plasma enhanced chemical vapor deposition (PECVD) (LPCVD), atmospheric pressure CVD (SACVD), or atmospheric pressure CVD (APCVD), as well as a controlled introduction pressure (PEALD), a tuned introduction scheme (Pulsed Chemical Vapor Deposition ), Hot-wire chemical vapor deposition (HWCVD, catCVD), hot-wire atomic layer deposition (HWALD), or supercritical fluid-introduced deposition, or combinations thereof. For example, thermal CVD deposition is the preferred method when rapid growth, conformality, process-orientation, and lateral films are required. As another example, a thermal ALD deposition process is desirable when excellent conformality in films deposited on difficult surfaces (e.g., trenches, holes, vias) is desired.

The disclosed tungsten compound can be supplied in pure form or in a suitable solvent such as ethylbenzene, xylene, mesitylene, decane, dodecane and mixed solution. The above-described compounds may be diluted to various concentrations in the solvent. At least one of the pure tungsten compound or mixed solution is introduced into the reactor in the form of a vapor by conventional means such as tubing and / or flow meters. This vapor form can be purified by conventional vaporization steps, such as direct vaporization, distillation, or by bubbling, or by using a sublimator, such as the method disclosed in International Publication WO 2009/087609, ≪ / RTI > can be prepared by vaporizing the solution. The pure compound or mixed solution is fed to the vaporizer in a liquid state, where it is vaporized before being introduced into the reactor. In another specific embodiment, the carrier gas may be vaporized by passing the carrier gas through a vessel containing a pure compound or mixed solution, or by bubbling the carrier gas into the pure compound or mixed solution. The carrier gas may include, but is not limited to, Ar, He, N ₂ , and mixtures thereof. Bubbling with carrier gas may also remove dissolved oxygen present in the pure compound or mixed solution. The carrier gas and the compound are then introduced as vapor into the reactor.

Optionally, the container of the disclosed compound or mixed solution may be heated to a temperature such that the compound / mixed solution is in a liquid phase or has sufficient vapor pressure. The vessel may be maintained at a temperature in the range, for example, from about 0 ° C to 150 ° C. Methods that can control the amount of vaporized compound depending on the temperature of the vessel are known and are adjustable in this manner.

The reactor can be an enclosure or a chamber in an apparatus that performs the deposition process and can be a chamber or a chamber, for example, a parallel-plate reactor, a cold wall reactor, a high-temperature reactor, a single-wafer reactor, But are not limited to, various types of deposition systems under appropriate conditions to form a layer.

Generally, the reactor contains one or more substrates onto which a thin film is to be deposited. The at least one substrate may be a semiconductor, a photovoltaic cell, a flat panel, or any suitable substrate used in the fabrication of LCD-TFT devices. The substrate includes, but is not limited to, a silicon substrate, a silica substrate, a silicon nitride substrate, a silicon oxynitride substrate, a tungsten substrate, or a combination thereof. In addition, a substrate comprising tungsten or a noble metal (e.g., platinum, palladium, rhodium, or gold) may be used. The substrate may also be one or more layers of different materials already deposited thereon from a previous fabrication step.

The temperature and pressure in the reactor can be adjusted by suitable conditions to deposit the tungsten precursor compound on the substrate, i. E., After introducing the vaporized compound into the chamber, at least a portion of the vaporized compound in the chamber is deposited on the substrate to form a tungsten- And the like. For example, the pressure in the reactor can be maintained at from about 0.1 Pa to about 10 ⁵ Pa, more preferably from about 2.5 Pa to about 10 ³ Pa, as required depending on the deposition parameters. Likewise, the temperature in the reactor can be maintained at from about 20 캜 to about 600 캜, preferably from about 100 캜 to about 400 캜, or from about 20 캜 to about 150 캜.

The temperature of the reactor can be controlled by controlling the temperature of the substrate holder or by controlling the temperature of the reactor wall. The apparatus for heating the substrate may be a known apparatus. The reactor wall can be heated to a suitable temperature to obtain a film having the required physical state and composition at a sufficient growth rate. Exemplary temperature ranges at which the reactor wall can be heated are in the range of about 20 째 C to about 600 째 C and are not limited thereto. If a plasma deposition process is used, the deposition temperature may range from about 20 캜 to about 350 캜. As another example, if a thermal process is performed, the deposition temperature may range from about 200 ° C to about 600 ° C.

In addition to the disclosed tungsten compounds, reactive gases can be simultaneously introduced into the reactor. The reaction gas may include oxidizing agents such as O ₂ ; O ₃ ; H ₂ O; H ₂ O ₂ ; An oxygen containing radical such as O. or OH; NO; NO ₂ ; Carboxylic acids such as formic acid, acetic acid, propionic acid; N ₂ O or a radical species of a carboxylic acid; And mixtures thereof. Preferably the oxidizing agent is selected from the group consisting of O ₂ , O ₃ , H ₂ O, H ₂ O ₂ , an oxygen-containing radical thereof such as O. or OH, and mixtures thereof.

As another example, the reactive gas may include a reducing agent such as, for example, H ₂ , NH ₃ , SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , (CH ₃ ) ₂ SiH ₂ , (C ₂ H ₅ ) ₂ SiH ₂ , _{CH 3) SiH 3, (C} 2 H 5) SiH 3, phenyl _{silane, N 2 H 4, N (} SiH 3) 3, N (CH 3) H 2, N (C 2 H 5) H 2, N ( _{CH 3) 2 H, N (} C 2 H 5) 2 H, N (CH 3) 3, N (C 2 H 5) 3, (SiMe 3) 2 NH, (CH 3) HNNH 2, (CH 3) ₂ NNH ₂ , phenylhydrazine, N-containing molecules, B ₂ H ₆ , 9-borabicyclo [3,3,1] nonane, dihydrobenzene furan, pyrazoline, trimethylaluminum, dimethylzinc, diethylzinc Radical species, and mixtures thereof. Preferably, the reducing agent is H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, Si ₃ H ₈ , SiH ₂ Me ₂ , SiH ₂ Et ₂ , N (SiH ₃ ) ₃ ,

It can be treated by plasma to decompose the reactive gas into radical form. N ₂ can also be used as a reducing agent when treated with a plasma. For example, the plasma can be generated at a power in the range of about 50 W to about 500 W, preferably about 100 W to about 200 W. Plasma can be generated or present in the reactor itself. As another example, the plasma may be present at a location remote from the reactor, e. G., As a remotely located plasma system.

The deposition conditions in the chamber refer to conditions under which the tungsten compound and / or the reactive gas can form a tungsten-containing film on the substrate. In the embodiment, the reaction gas is treated with a plasma to form a tungsten- It is believed to be able to provide energy.

Depending on what type of film is deposited, a secondary precursor can be introduced into the reactor. The second precursor includes another elemental source such as silicon, copper, praseodymium, manganese, ruthenium, titanium, tantalum, bismuth, zirconium, hafnium, lead, niobium, magnesium, aluminum, lanthanum or mixtures thereof. When a secondary precursor is used, the resulting film deposited on the substrate may contain two or more different elements. The tungsten compound and the reactive gas may be simultaneously introduced into the reactor (chemical vapor deposition), sequentially (atomic layer deposition) or a different combination thereof. The reactor can be purged with an inert gas between the introduction of the compound and the introduction of the reaction gas. Alternatively, the reactive gas and compound may be mixed together to form a reactive gas / compound mixture, and then introduced into the reactor as a mixture. Another example is the introduction of a reactive gas continuously and the introduction of one or more tungsten compounds by pulses (pulsed chemical vapor deposition).

The vaporized precursor and the reactive gas may be pulsed into the reactor sequentially or simultaneously (pulsed CVD). Each precursor pulse may last for a period ranging from about 0.01 seconds to about 10 seconds, preferably from about 0.3 seconds to about 3 seconds, and more preferably from about 0.5 seconds to about 2 seconds. In another aspect, the reactive gas may also be pulsed into the reactor. In this example, the pulse of each gas may last in the range of about 0.01 seconds to about 10 seconds, or about 0.3 seconds to about 3 seconds, preferably about 0.5 seconds to about 2 seconds.

The deposition can be performed by varying the time according to the specific process conditions. In general, the deposition can be repeatedly carried out as necessary to produce a film having the required properties. Typical film thicknesses can range from a few angstroms to hundreds of microns depending on the particular deposition process. The deposition process can be repeated as many times as necessary.

The vapor phase of the tungsten compound disclosed in one exemplary CVD-type process and the reactive gas are simultaneously introduced into the reactor and not limited thereto. The two are reacted and deposited on a substrate with a tungsten containing film. In this exemplary CVD process, when the reactive gas is treated with a plasma, the CVD process becomes a typical PECVD process. The reaction gas may be subsequently treated with the plasma before or after the subsequent introduction into the chamber.

One vapor phase of the tungsten compound disclosed in one non-limiting ALD type process is introduced into the reactor, wherein the conditions are suitable for reacting the compound with the substrate. The excess compound can then be removed from the reactor by purging it in the reactor and emptying it. A reducing agent (e. G., H ₂ ) is introduced into the reactor where it reacts with the deposited compound in a self limiting manner. Any excess reducing agent is removed from the reactor by purging and emptying in the reactor. If the required film is a tungsten film, this two step process can be repeated until a film having the required thickness is provided or a film having the required thickness is obtained.

Alternatively, if the required film contains two elements, the vapor of the second precursor may be introduced into the reactor after the two step process. The secondary precursor will be selected based on the secondary elements required in the film to be deposited. A second precursor is introduced into the reactor wherein the conditions are suitable for reacting the second precursor with the deposited tungsten layer. Any excess secondary precursor is removed from the reactor by purging and evacuating the reactor. Once again, the reducing agent may be introduced into the reactor to react with the deposited secondary precursor. The excess reducing agent is removed from the reactor by purging and evacuating the reactor. Once the required film thickness is achieved, the process can be terminated. However, if a thicker film is required, a total of four steps can be repeated. By alternately providing a tungsten compound, a second precursor, and a reactive gas, films of the required composition and thickness can be deposited.

In this typical ALD process, a typical ALD process becomes a typical PEALD process when the reactive gas is treated with a plasma. The reaction gas may be subsequently treated with plasma before or after introduction into the chamber.

The tungsten-containing film produced from the process described above can be used in the production of films of pure tungsten (W), tungsten nitride (WN), tungsten carbide (WC), tungsten carbide (WCN), silicide tungsten (WkSil) or tungsten oxide (Where k, l, m, and n are integers ranging from 1 to 6 inclusive). A suitable tungsten compound, a selective secondary precursor, and a reactive gas may be selected as needed to obtain the film composition required.

When obtaining the required film thickness, the film may be introduced into further processing, such as thermal annealing, furnace-annealing, rapid thermal annealing, UV or e-beam curing, and / or plasma gas exposure. For example, the tungsten-containing film may be in the range of from about 200 ° C to about 1000 ° C for a time in the range of about 0.1 seconds to about 7200 seconds under an inert atmosphere, an H-containing atmosphere, an N-containing atmosphere, an O- Lt; / RTI > Most preferably, the temperature is 400 DEG C for 3600 seconds under an H-containing atmosphere. The resulting film contains less impurities and thus has an improved density and can produce improved leakage currents. The annealing step may be performed in the same reaction chamber in which the deposition process is performed. Alternatively, the substrate may be removed from the reaction chamber, and the annealing / flash annealing process is performed in a separate apparatus. Any of the above post-treatment methods, particularly thermal annealing, can reduce carbon and nitrogen contamination of the tungsten-containing film. Which in turn tends to improve the resistance of the film.

The tungsten containing film deposited by any of the processes disclosed after annealing has a thickness of from about 5.5 mu ohm.cm to about 70 mu ohm.cm, preferably from about 5.5 mu ohm.cm to about 20 mu ohm.cm, more preferably about 5.5 mu ohm.cm. cm < 2 > to about 12 mu m. cm. The room temperature is from about 20 [deg.] C to about 28 [deg.] C, depending on the season.

Bulk resistors are also known as bulk resistors. It is known that the bulk resistance is measured at room temperature on a W film, generally about 50 nm thick. The bulk resistance increases with thinner films due to changes in the electron transport mechanism and increases at higher temperatures.

Hereinafter, synthesis examples of the compound represented by the formula (1) contained in the precursor of the present invention and production examples of the film using the same will be specifically described, but the present invention is not limited to these examples.

Example 1 Synthesis of (t-Bu-N =) ₂ W (Me-CO = CH-CMe = N-iPr) ₂

In a round bottom flask under nitrogen, 10 g (25.2 mmole) of WCl 6 and 16.5 g (113.5 mmole) of n-butyltrimethylsilylamine were reacted overnight in 100 mL of anhydrous THF to obtain a yellow solid. To the yellow solid was added 10 mL of pyridine and the mixture was stirred for 2 hours to obtain a black solid. A solution of 0.95 mL (1.8 mmole) of n-butyllithium in 0.25 g (1.8 mmole) of Me-CO = CH-CMe = N-iPr ligand at -78 캜 was added dropwise at -78 캜 to the tungsten compound (75% yield) of a yellow solid. The NMR ¹ H shift and ¹³ C shift (t-Bu-N) were carried out overnight at room temperature. = ₂ W (Me-CO = CH-CMe = N-iPr) ₂ .

R ^a -CO-CR ^b = CO-R ^c R ^a R ^b R ^c One Me H Me 2 Me H Meat 3 Me H i-Pr 4 Me H CF ₃ 5 Meat H Me 6 Meat H Meat 7 Meat H i-Pr 8 Meat H CF ₃ 9 i-Pr H Me 10 i-Pr H Meat 11 i-Pr H i-Pr 12 i-Pr H CF ₃ 13 CF ₃ H Me 14 CF ₃ H Meat 15 CF ₃ H i-Pr 16 CF ₃ H CF ₃

R ^a --CO - CR ^b --CR ^c = NR ^d R ^a R ^b R ^c R ^d 17 Me H Me Me 18 Me H Me Meat 19 Me H Me i-Pr 20 Me H Meat Me 21 Me H Meat Meat 22 Me H Meat iPr 23 Me H i-Pr Me 24 Me H i-Pr Meat 25 Me H i-Pr i-Pr 26 Me H CF ₃ Me 27 Me H CF ₃ Meat 28 Me H CF ₃ i-Pr 29 Meat H Me Me 30 Meat H Me Meat 31 Meat H Me i-Pr 32 Meat H Meat Me 33 Meat H Meat Meat 34 Meat H Meat i-Pr 35 Meat H i-Pr Me 36 Meat H i-Pr Meat 37 Meat H i-Pr i-Pr 38 Meat H CF ₃ Me 39 Meat H CF ₃ Meat 40 Meat H CF ₃ i-Pr 41 i-Pr H Me Me 42 i-Pr H Me Meat 43 i-Pr H Me i-Pr 44 i-Pr H Meat Me 45 i-Pr H Meat Meat 46 i-Pr H Meat iPr 47 i-Pr H i-Pr Me 48 i-Pr H i-Pr Meat 49 i-Pr H i-Pr i-Pr 50 i-Pr H CF ₃ Me 51 i-Pr H CF ₃ Meat 52 i-Pr H CF ₃ i-Pr 53 CF ₃ H Me Me 54 CF ₃ H Me Meat 55 CF ₃ H Me i-Pr 56 CF ₃ H Meat Me 57 CF ₃ H Meat Meat 58 CF ₃ H Meat i-Pr 59 CF ₃ H i-Pr Me 60 CF ₃ H i-Pr Meat 61 CF ₃ H i-Pr i-Pr 62 CF ₃ H CF ₃ Me 63 CF ₃ H CF ₃ Meat 64 CF ₃ H CF ₃ i-Pr

R ^a -N = CR ^b -CR ^c = CR ^d -NR ^e R ^a R ^b R ^c R ^d R ^e 65 Me Me H Me Me 66 Me Me H Me Meat 67 Me Me H Me i-Pr 68 Me Me H Meat Me 69 Me Me H Meat Meat 70 Me Me H Meat i-Pr 71 Me Me H i-Pr Me 72 Me Me H i-Pr Meat 73 Me Me H i-Pr i-Pr 74 Me Me H CF ₃ Me 75 Me Me H CF ₃ Meat 76 Me Me H CF ₃ i-Pr 77 Me Meat H Me Me 78 Me Meat H Me Meat 79 Me Meat H Me i-Pr 80 Me Meat H Meat Me 81 Me Meat H Meat Meat 82 Me Meat H Meat i-Pr 83 Me Meat H i-Pr Me 84 Me Meat H i-Pr Meat 85 Me Meat H i-Pr i-Pr 86 Me Meat H CF ₃ Me 87 Me Meat H CF ₃ Meat 88 Me Meat H CF ₃ i-Pr 89 Me i-Pr H Me Me 90 Me i-Pr H Me Meat 91 Me i-Pr H Me i-Pr 92 Me i-Pr H Meat Me 93 Me i-Pr H Meat Meat 94 Me i-Pr H Meat i-Pr 95 Me i-Pr H i-Pr Me 96 Me i-Pr H i-Pr Meat 97 Me i-Pr H i-Pr i-Pr 98 Me i-Pr H CF3 Me 99 Me i-Pr H CF3 Meat 100 Me i-Pr H CF3 i-Pr 101 Me CF ₃ H Me Me 102 Me CF ₃ H Me Meat 103 Me CF ₃ H Me i-Pr 104 Me CF ₃ H Meat Me 105 Me CF ₃ H Meat Meat 106 Me CF ₃ H Meat i-Pr 107 Me CF ₃ H i-Pr Me 108 Me CF ₃ H i-Pr Meat 109 Me CF ₃ H i-Pr i-Pr 110 Me CF ₃ H CF ₃ Me 111 Me CF ₃ H CF ₃ Meat 112 Me CF ₃ H CF ₃ i-Pr 113 Meat Me H Me Me 114 Meat Me H Me Meat 115 Meat Me H Me i-Pr 116 Meat Me H Meat Me 117 Meat Me H Meat Meat 118 Meat Me H Meat i-Pr 119 Meat Me H i-Pr Me 120 Meat Me H i-Pr Meat 121 Meat Me H i-Pr i-Pr 122 Meat Me H CF ₃ Me 123 Meat Me H CF ₃ Meat 124 Meat Me H CF ₃ i-Pr 125 Meat Meat H Me Me 126 Meat Meat H Me Meat 127 Meat Meat H Me i-Pr 128 Meat Meat H Meat Me 129 Meat Meat H Meat Meat 130 Meat Meat H Meat i-Pr 131 Meat Meat H i-Pr Me 132 Meat Meat H i-Pr Meat 133 Meat Meat H i-Pr i-Pr 134 Meat Meat H CF ₃ Me 135 Meat Meat H CF ₃ Meat 136 Meat Meat H CF ₃ i-Pr 137 Meat i-Pr H Me Me 138 Meat i-Pr H Me Meat 139 Meat i-Pr H Me i-Pr 140 Meat i-Pr H Meat Me 141 Meat i-Pr H Meat Meat 142 Meat i-Pr H Meat i-Pr 143 Meat i-Pr H i-Pr Me 144 Meat i-Pr H i-Pr Meat 145 Meat i-Pr H i-Pr i-Pr 146 Meat i-Pr H CF ₃ Me 147 Meat i-Pr H CF ₃ Meat 148 Meat i-Pr H CF ₃ i-Pr 149 Meat CF ₃ H Me Me 150 Meat CF ₃ H Me Meat 151 Meat CF ₃ H Me i-Pr 152 Meat CF ₃ H Meat Me 153 Meat CF ₃ H Meat Meat 154 Meat CF ₃ H Meat i-Pr 155 Meat CF ₃ H i-Pr Me 156 Meat CF ₃ H i-Pr Meat 157 Meat CF ₃ H i-Pr i-Pr 158 Meat CF ₃ H CF ₃ Me 159 Meat CF ₃ H CF ₃ Meat 160 Meat CF ₃ H CF ₃ i-Pr 161 i-Pr Me H Me Me 162 i-Pr Me H Me Meat 163 i-Pr Me H Me i-Pr 164 i-Pr Me H Meat Me 165 i-Pr Me H Meat Meat 166 i-Pr Me H Meat i-Pr 167 i-Pr Me H i-Pr Me 168 i-Pr Me H i-Pr Meat 169 i-Pr Me H i-Pr i-Pr 170 i-Pr Me H CF3 Me 171 i-Pr Me H CF3 Meat 172 i-Pr Me H CF3 i-Pr 173 i-Pr Meat H Me Me 174 i-Pr Meat H Me Meat 175 i-Pr Meat H Me i-Pr 176 i-Pr Meat H Meat Me 177 i-Pr Meat H Meat Meat 178 i-Pr Meat H Meat i-Pr 179 i-Pr Meat H i-Pr Me 180 i-Pr Meat H i-Pr Meat 181 i-Pr Meat H i-Pr i-Pr 182 i-Pr Meat H CF ₃ Me 183 i-Pr Meat H CF ₃ Meat 184 i-Pr Meat H CF ₃ i-Pr 185 i-Pr i-Pr H Me Me 186 i-Pr i-Pr H Me Meat 187 i-Pr i-Pr H Me i-Pr 188 i-Pr i-Pr H Meat Me 189 i-Pr i-Pr H Meat Meat 190 i-Pr i-Pr H Meat i-Pr 191 i-Pr i-Pr H i-Pr Me 192 i-Pr i-Pr H i-Pr Meat 193 i-Pr i-Pr H i-Pr i-Pr 194 i-Pr i-Pr H CF ₃ Me 195 i-Pr i-Pr H CF ₃ Meat 196 i-Pr i-Pr H CF ₃ i-Pr 197 i-Pr CF ₃ H Me Me 198 i-Pr CF ₃ H Me Meat 199 i-Pr CF ₃ H Me i-Pr 200 i-Pr CF ₃ H Meat Me 201 i-Pr CF ₃ H Meat Meat 202 i-Pr CF ₃ H Meat i-Pr 203 i-Pr CF ₃ H i-Pr Me 204 i-Pr CF ₃ H i-Pr Meat 205 i-Pr CF ₃ H i-Pr i-Pr 206 i-Pr CF ₃ H CF ₃ Me 207 i-Pr CF ₃ H CF ₃ Meat 208 i-Pr CF ₃ H CF ₃ i-Pr

R ^a -N = CR ^b -CR ^c -NR ^d R ^a R ^b R ^c R ^d 209 Me H H Me 210 Me H H Meat 211 Me H H i-Pr 212 Me Me Me Me 213 Me Me Me Meat 214 Me Me Me i-Pr 215 Me Me Meat Me 216 Me Me Meat Meat 217 Me Me Meat i-Pr 218 Me Me i-Pr Me 219 Me Me i-Pr Meat 220 Me Me i-Pr i-Pr 221 Me Me CF ₃ Me 222 Me Me CF ₃ Meat 223 Me Me CF ₃ i-Pr 224 Me Meat Me Me 225 Me Meat Me Meat 226 Me Meat Me i-Pr 227 Me Meat Meat Me 228 Me Meat Meat Meat 229 Me Meat Meat i-Pr 230 Me Meat i-Pr Me 231 Me Meat i-Pr Meat 232 Me Meat i-Pr i-Pr 233 Me Meat CF ₃ Me 234 Me Meat CF ₃ Meat 235 Me Meat CF ₃ i-Pr 236 Me i-Pr Me Me 237 Me i-Pr Me Meat 238 Me i-Pr Me i-Pr 239 Me i-Pr Meat Me 240 Me i-Pr Meat Meat 241 Me i-Pr Meat i-Pr 242 Me i-Pr i-Pr Me 243 Me i-Pr i-Pr Meat 244 Me i-Pr i-Pr i-Pr 245 Me i-Pr CF ₃ Me 246 Me i-Pr CF ₃ Meat 247 Me i-Pr CF ₃ i-Pr 248 Me CF ₃ Me Me 249 Me CF ₃ Me Meat 250 Me CF ₃ Me i-Pr 260 Me CF ₃ Meat Me 261 Me CF ₃ Meat Meat 262 Me CF ₃ Meat i-Pr 263 Me CF ₃ i-Pr Me 264 Me CF ₃ i-Pr Meat 265 Me CF ₃ i-Pr i-Pr 266 Me CF ₃ CF ₃ Me 267 Me CF ₃ CF ₃ Meat 268 Me CF ₃ CF ₃ i-Pr 269 Meat H H Me 270 Meat H H Meat 271 Meat H H i-Pr 272 Meat Me Me Me 273 Meat Me Me Meat 274 Meat Me Me i-Pr 275 Meat Me Meat Me 276 Meat Me Meat Meat 277 Meat Me Meat i-Pr 278 Meat Me i-Pr Me 279 Meat Me i-Pr Meat 280 Meat Me i-Pr i-Pr 281 Meat Me CF3 Me 282 Meat Me CF3 Meat 283 Meat Me CF3 iPr 284 Meat Meat Me Me 285 Meat Meat Me Meat 286 Meat Meat Me iPr 287 Meat Meat Meat Me 288 Meat Meat Meat Meat 289 Meat Meat Meat i-Pr 290 Meat Meat i-Pr Me 291 Meat Meat i-Pr Meat 292 Meat Meat i-Pr i-Pr 293 Meat Meat CF ₃ Me 294 Meat Meat CF ₃ Meat 295 Meat Meat CF ₃ i-Pr 296 Meat i-Pr Me Me 297 Meat i-Pr Me Meat 298 Meat i-Pr Me i-Pr 299 Meat i-Pr Meat Me 300 Meat i-Pr Meat Meat 301 Meat i-Pr Meat i-Pr 302 Meat i-Pr i-Pr Me 303 Meat i-Pr i-Pr Meat 304 Meat i-Pr i-Pr i-Pr 305 Meat i-Pr CF ₃ Me 306 Meat i-Pr CF ₃ Meat 307 Meat i-Pr CF ₃ i-Pr 308 Meat CF ₃ Me Me 309 Meat CF ₃ Me Meat 310 Meat CF ₃ Me i-Pr 311 Meat CF ₃ Meat Me 312 Meat CF ₃ Meat Meat 313 Meat CF ₃ Meat i-Pr 314 Meat CF ₃ i-Pr Me 315 Meat CF ₃ i-Pr Meat 316 Meat CF ₃ i-Pr i-Pr 317 Meat CF ₃ CF ₃ Me 318 Meat CF ₃ CF ₃ Meat 319 Meat CF ₃ CF ₃ i-Pr 320 i-Pr H H Me 321 i-Pr H H Meat 322 i-Pr H H i-Pr 323 i-Pr Me Me Me 324 i-Pr Me Me Meat 325 i-Pr Me Me i-Pr 326 i-Pr Me Meat Me 327 i-Pr Me Meat Meat 328 i-Pr Me Meat i-Pr 329 i-Pr Me i-Pr Me 330 i-Pr Me i-Pr Meat 331 i-Pr Me i-Pr i-Pr 332 i-Pr Me CF ₃ Me 333 i-Pr Me CF ₃ Meat 334 i-Pr Me CF ₃ i-Pr 335 i-Pr Meat Me Me 336 i-Pr Meat Me Meat 337 i-Pr Meat Me i-Pr 338 i-Pr Meat Meat Me 339 i-Pr Meat Meat Meat 340 i-Pr Meat Meat i-Pr 341 i-Pr Meat i-Pr Me 342 i-Pr Meat i-Pr Meat 343 i-Pr Meat i-Pr i-Pr 344 i-Pr Meat CF ₃ Me 345 i-Pr Meat CF ₃ Meat 346 i-Pr Meat CF ₃ i-Pr 347 i-Pr i-Pr Me Me 348 i-Pr i-Pr Me Meat 349 i-Pr i-Pr Me i-Pr 350 i-Pr i-Pr Meat Me 351 i-Pr i-Pr Meat Meat 352 i-Pr i-Pr Meat i-Pr 353 i-Pr i-Pr i-Pr Me 354 i-Pr i-Pr i-Pr Meat 355 i-Pr i-Pr i-Pr i-Pr 356 i-Pr i-Pr CF ₃ Me 357 i-Pr i-Pr CF ₃ Meat 358 i-Pr i-Pr CF ₃ i-Pr 359 i-Pr CF ₃ Me Me 360 i-Pr CF ₃ Me Meat 361 i-Pr CF ₃ Me i-Pr 362 i-Pr CF ₃ Meat Me 363 i-Pr CF ₃ Meat Meat 364 i-Pr CF ₃ Meat i-Pr 365 i-Pr CF ₃ i-Pr Me 366 i-Pr CF ₃ i-Pr Meat 367 i-Pr CF ₃ i-Pr i-Pr 368 i-Pr CF ₃ CF ₃ Me 369 i-Pr CF ₃ CF ₃ Meat 370 i-Pr CF ₃ CF ₃ i-Pr

R ^a -N = CR ^b -NR ^c R ^d R ^a R ^b R ^c R ^d 371 Me H H Me 372 Me H H Meat 373 Me H H i-Pr 374 Me H Me Me 375 Me H Me Meat 376 Me H Me i-Pr 377 Me H Meat Meat 378 Me H Meat i-Pr 379 Me H i-Pr i-Pr 380 Me Me Me Me 381 Me Me Me Meat 382 Me Me Me i-Pr 383 Me Me Meat Meat 384 Me Me Meat i-Pr 385 Me Me i-Pr i-Pr 386 Me Me CF ₃ Me 387 Me Me CF ₃ Meat 388 Me Me CF ₃ i-Pr 389 Me Meat Me Me 390 Me Meat Me Meat 391 Me Meat Me i-Pr 392 Me Meat Meat Meat 393 Me Meat Meat i-Pr 394 Me Meat i-Pr i-Pr 395 Me Meat CF ₃ Me 396 Me Meat CF ₃ Meat 397 Me Meat CF ₃ i-Pr 398 Me i-Pr Me Me 399 Me i-Pr Me Meat 400 Me i-Pr Me i-Pr 401 Me i-Pr Meat Meat 402 Me i-Pr Meat i-Pr 403 Me i-Pr i-Pr i-Pr 404 Me i-Pr CF ₃ Me 405 Me i-Pr CF ₃ Meat 406 Me i-Pr CF ₃ i-Pr 407 Me CF ₃ Me Me 408 Me CF ₃ Me Meat 409 Me CF ₃ Me i-Pr 410 Me CF ₃ Meat Meat 411 Me CF ₃ Meat i-Pr 412 Me CF ₃ i-Pr i-Pr 413 Me CF ₃ CF ₃ Me 414 Me CF ₃ CF ₃ Meat 415 Me CF ₃ CF ₃ i-Pr 416 Meat H H Me 417 Meat H H Meat 418 Meat H H i-Pr 419 Meat H Me Me 420 Meat H Me Meat 421 Meat H Me i-Pr 422 Meat H Meat Meat 423 Meat H Meat i-Pr 424 Meat H i-Pr i-Pr 425 Meat Me Me Me 426 Meat Me Me Meat 427 Meat Me Me i-Pr 428 Meat Me Meat Meat 429 Meat Me Meat i-Pr 430 Meat Me i-Pr i-Pr 431 Meat Me CF ₃ Me 432 Meat Me CF ₃ Meat 433 Meat Me CF ₃ i-Pr 434 Meat Meat Me Me 435 Meat Meat Me Meat 436 Meat Meat Me i-Pr 437 Meat Meat Meat Meat 438 Meat Meat Meat i-Pr 439 Meat Meat i-Pr i-Pr 440 Meat Meat CF ₃ Me 441 Meat Meat CF ₃ Meat 442 Meat Meat CF ₃ iPr 443 Meat i-Pr Me Me 444 Meat i-Pr Me Meat 445 Meat i-Pr Me i-Pr 446 Meat i-Pr Meat Meat 447 Meat i-Pr Meat i-Pr 448 Meat i-Pr i-Pr i-Pr 449 Meat i-Pr CF ₃ Me 450 Meat i-Pr CF ₃ Meat 451 Meat i-Pr CF ₃ i-Pr 452 Meat CF ₃ Me Me 453 Meat CF ₃ Me Meat 454 Meat CF ₃ Me i-Pr 455 Meat CF ₃ Meat Meat 456 Meat CF ₃ Meat i-Pr 457 Meat CF ₃ i-Pr i-Pr 458 Meat CF ₃ CF ₃ Me 459 Meat CF ₃ CF ₃ Meat 460 Meat CF ₃ CF ₃ i-Pr 461 i-Pr H H Me 462 i-Pr H H Meat 463 i-Pr H H i-Pr 464 i-Pr H Me Me 465 i-Pr H Me Meat 466 i-Pr H Me i-Pr 467 i-Pr H Meat Meat 468 i-Pr H Meat i-Pr 469 i-Pr H i-Pr i-Pr 470 i-Pr Me Me Me 471 i-Pr Me Me Meat 472 i-Pr Me Me i-Pr 473 i-Pr Me Meat Meat 474 i-Pr Me Meat i-Pr 475 i-Pr Me i-Pr i-Pr 476 i-Pr Me CF ₃ Me 477 i-Pr Me CF ₃ Meat 478 i-Pr Me CF ₃ i-Pr 479 i-Pr Meat Me Me 480 i-Pr Meat Me Meat 481 i-Pr Meat Me i-Pr 482 i-Pr Meat Meat Meat 483 i-Pr Meat Meat i-Pr 484 i-Pr Meat i-Pr i-Pr 485 i-Pr Meat CF ₃ Me 486 i-Pr Meat CF ₃ Meat 487 i-Pr Meat CF ₃ i-Pr 488 i-Pr i-Pr Me Me 489 i-Pr i-Pr Me Meat 490 i-Pr i-Pr Me i-Pr 491 i-Pr i-Pr Meat Meat 492 i-Pr i-Pr Meat i-Pr 493 i-Pr i-Pr i-Pr i-Pr 494 i-Pr i-Pr CF ₃ Me 495 i-Pr i-Pr CF ₃ Meat 496 i-Pr i-Pr CF ₃ i-Pr 497 i-Pr CF ₃ Me Me 498 i-Pr CF ₃ Me Meat 499 i-Pr CF ₃ Me i-Pr 500 i-Pr CF ₃ Meat Meat 501 i-Pr CF ₃ Meat i-Pr 502 i-Pr CF ₃ i-Pr i-Pr 503 i-Pr CF ₃ CF ₃ Me 504 i-Pr CF ₃ CF ₃ Meat 505 i-Pr CF ₃ CF ₃ i-Pr

R ^a -N = C (-NR ^b R ^c ) -NR ^d R ^e R ^a R ^b R ^c R ^d R ^e 506 H H H H H 507 H H H H Me 508 H H H H Meat 509 H H H H i-Pr 510 H H H Me Me 511 H H H Me Meat 512 H H H Me i-Pr 513 H H H Meat Meat 514 H H H Meat i-Pr 515 H H H i-Pr i-Pr 516 H H Me H Me 517 H H Me H Meat 518 H H Me H i-Pr 519 H H Me Me Me 520 H H Me Me Meat 521 H H Me Me i-Pr 522 H H Me Meat Meat 523 H H Me Meat i-Pr 524 H H Me i-Pr i-Pr 525 H H Meat H Me 526 H H Meat H Meat 527 H H Meat H i-Pr 528 H H Meat Me Me 529 H H Meat Me Meat 530 H H Meat Me i-Pr 531 H H Meat Meat Meat 532 H H Meat Meat i-Pr 533 H H Meat i-Pr i-Pr 534 H H i-Pr H Me 535 H H i-Pr H Meat 536 H H i-Pr H i-Pr 537 H H i-Pr Me Me 538 H H i-Pr Me Meat 539 H H i-Pr Me i-Pr 540 H H i-Pr Meat Meat 541 H H i-Pr Meat i-Pr 542 H H i-Pr i-Pr i-Pr 543 H Me Me H Me 544 H Me Me H Meat 545 H Me Me H i-Pr 546 H Me Me Me Me 547 H Me Me Me Meat 548 H Me Me Me i-Pr 549 H Me Me Meat Meat 550 H Me Me Meat i-Pr 551 H Me Me i-Pr i-Pr 552 H Me Meat H Me 553 H Me Meat H Meat 554 H Me Meat H i-Pr 555 H Me Meat Me Me 556 H Me Meat Me Meat 557 H Me Meat Me i-Pr 558 H Me Meat Meat Meat 559 H Me Meat Meat i-Pr 560 H Me Meat i-Pr i-Pr 561 H Me i-Pr H Me 562 H Me i-Pr H Meat 563 H Me i-Pr H i-Pr 564 H Me i-Pr Me Me 565 H Me i-Pr Me Meat 566 H Me i-Pr Me i-Pr 567 H Me i-Pr Meat Meat 568 H Me i-Pr Meat i-Pr 569 H Me i-Pr i-Pr i-Pr 570 H Meat Meat H Me 571 H Meat Meat H Meat 572 H Meat Meat H i-Pr 573 H Meat Meat Me Me 574 H Meat Meat Me Meat 575 H Meat Meat Me i-Pr 576 H Meat Meat Meat Meat 577 H Meat Meat Meat i-Pr 578 H Meat Meat i-Pr i-Pr 579 H Meat i-Pr H Me 580 H Meat i-Pr H Meat 581 H Meat i-Pr H i-Pr 582 H Meat i-Pr Me Me 583 H Meat i-Pr Me Meat 584 H Meat i-Pr Me i-Pr 585 H Meat i-Pr Meat Meat 586 H Meat i-Pr Meat i-Pr 587 H Meat i-Pr i-Pr i-Pr 588 H i-Pr Meat H Me 589 H i-Pr i-Pr H Me 590 H i-Pr i-Pr H Meat 591 H i-Pr i-Pr H i-Pr 592 H i-Pr i-Pr Me Me 593 H i-Pr i-Pr Me Meat 594 H i-Pr i-Pr Me i-Pr 595 H i-Pr i-Pr Meat Meat 596 H i-Pr i-Pr Meat i-Pr 597 H i-Pr i-Pr i-Pr i-Pr 598 Me H H H H 599 Me H H H Me 600 Me H H H Meat 601 Me H H H i-Pr 602 Me H H Me Me 603 Me H H Me i-Pr 604 Me H H Me i-Pr 605 Me H H Meat Meat 606 Me H H Meat i-Pr 607 Me H H i-Pr i-Pr 608 Me H Me H Me 609 Me H Me H Meat 610 Me H Me H i-Pr 611 Me H Me Me Me 612 Me H Me Me Meat 613 Me H Me Me i-Pr 614 Me H Me Meat Meat 615 Me H Me Meat i-Pr 616 Me H Me i-Pr i-Pr 617 Me H Meat H Me 618 Me H Meat H Meat 619 Me H Meat H i-Pr 620 Me H Meat Me Me 621 Me H Meat Me Meat 622 Me H Meat Me i-Pr 623 Me H Meat Meat Meat 624 Me H Meat Meat i-Pr 625 Me H Meat i-Pr i-Pr 626 Me H i-Pr H Me 527 Me H i-Pr H Meat 628 Me H i-Pr H i-Pr 629 Me H i-Pr Me Me 630 Me H i-Pr Me Meat 631 Me H i-Pr Me i-Pr 632 Me H i-Pr Meat Meat 633 Me H i-Pr Meat i-Pr 634 Me H i-Pr i-Pr i-Pr 635 Me Me Me H Me 636 Me Me Me H Meat 637 Me Me Me H i-Pr 638 Me Me Me Me Me 639 Me Me Me Me Meat 640 Me Me Me Me i-Pr 641 Me Me Me Meat Meat 642 Me Me Me Meat i-Pr 643 Me Me Me i-Pr i-Pr 644 Me Me Meat H Me 645 Me Me Meat H Meat 646 Me Me Meat H i-Pr 647 Me Me Meat Me Me 648 Me Me Meat Me Meat 649 Me Me Meat Me iPr 650 Me Me Meat Meat Meat 651 Me Me Meat Meat i-Pr 652 Me Me Meat i-Pr i-Pr 653 Me Me i-Pr H Me 654 Me Me i-Pr H Meat 655 Me Me i-Pr H i-Pr 656 Me Me i-Pr Me Me 657 Me Me i-Pr Me Meat 658 Me Me i-Pr Me i-Pr 659 Me Me i-Pr Meat Meat 660 Me Me i-Pr Meat i-Pr 661 Me Me i-Pr i-Pr i-Pr 662 Me Meat Meat H Me 663 Me Meat Meat H Meat 664 Me Meat Meat H iPr 665 Me Meat Meat Me Me 666 Me Meat Meat Me Meat 667 Me Meat Meat Me iPr 668 Me Meat Meat Meat Meat 669 Me Meat Meat Meat i-Pr 670 Me Meat Meat i-Pr i-Pr 671 Me Meat i-Pr H Me 672 Me Meat i-Pr H Meat 673 Me Meat i-Pr H i-Pr 674 Me Meat i-Pr Me Me 675 Me Meat i-Pr Me Meat 676 Me Meat i-Pr Me i-Pr 678 Me Meat i-Pr Meat Meat 679 Me Meat i-Pr Meat i-Pr 680 Me Meat i-Pr i-Pr i-Pr 681 Me i-Pr Meat H Me 682 Me i-Pr i-Pr H Me 683 Me i-Pr i-Pr H Meat 684 Me i-Pr i-Pr H i-Pr 685 Me i-Pr i-Pr Me Me 686 Me i-Pr i-Pr Me Meat 687 Me i-Pr i-Pr Me i-Pr 688 Me i-Pr i-Pr Meat Meat 689 Me i-Pr i-Pr Meat i-Pr 690 Me i-Pr i-Pr i-Pr i-Pr 691 Meat H H H H 692 Meat H H H Me 693 Meat H H H Meat 694 Meat H H H i-Pr 695 Meat H H Me Me 696 Meat H H Me Meat 697 Meat H H Me i-Pr 698 Meat H H Meat Meat 699 Meat H H Meat iPr 700 Meat H H iPr iPr 701 Meat H Me H Me 702 Meat H Me H Meat 703 Meat H Me H i-Pr 704 Meat H Me Me Me 705 Meat H Me Me Meat 706 Meat H Me Me i-Pr 707 Meat H Me Meat Meat 708 Meat H Me Meat i-Pr 709 Meat H Me i-Pr i-Pr 710 Meat H Meat H Me 711 Meat H Meat H Meat 712 Meat H Meat H i-Pr 713 Meat H Meat Me Me 714 Meat H Meat Me Meat 715 Meat H Meat Me i-Pr 716 Meat H Meat Meat Meat 717 Meat H Meat Meat i-Pr 718 Meat H Meat i-Pr i-Pr 719 Meat H i-Pr H Me 720 Meat H i-Pr H Meat 721 Meat H i-Pr H i-Pr 722 Meat H i-Pr Me Me 723 Meat H i-Pr Me Meat 724 Meat H i-Pr Me i-Pr 725 Meat H i-Pr Meat Meat 726 Meat H i-Pr Meat i-Pr 727 Meat H i-Pr i-Pr i-Pr 728 Meat Me Me H Me 729 Meat Me Me H Meat 730 Meat Me Me H i-Pr 731 Meat Me Me Me Me 732 Meat Me Me Me Meat 733 Meat Me Me Me i-Pr 734 Meat Me Me Meat Meat 735 Meat Me Me Meat i-Pr 736 Meat Me Me i-Pr i-Pr 737 Meat Me Meat H Me 738 Meat Me Meat H Meat 739 Meat Me Meat H i-Pr 740 Meat Me Meat Me Me 741 Meat Me Meat Me Meat 742 Meat Me Meat Me i-Pr 743 Meat Me Meat Meat Meat 744 Meat Me Meat Meat i-Pr 745 Meat Me Meat i-Pr i-Pr 746 Meat Me i-Pr H Me 747 Meat Me i-Pr H Meat 748 Meat Me i-Pr H i-Pr 749 Meat Me i-Pr Me Me 750 Meat Me i-Pr Me Meat 751 Meat Me i-Pr Me i-Pr 752 Meat Me i-Pr Meat Meat 753 Meat Me i-Pr Meat i-Pr 754 Meat Me i-Pr i-Pr i-Pr 755 Meat Meat Meat H Me 756 Meat Meat Meat H Meat 757 Meat Meat Meat H i-Pr 758 Meat Meat Meat Me Me 759 Meat Meat Meat Me Meat 760 Meat Meat Meat Me i-Pr 761 Meat Meat Meat Meat Meat 762 Meat Meat Meat Meat i-Pr 763 Meat Meat Meat i-Pr i-Pr 764 Meat Meat i-Pr H Me 765 Meat Meat i-Pr H Meat 766 Meat Meat i-Pr H i-Pr 767 Meat Meat i-Pr Me Me 768 Meat Meat i-Pr Me Meat 769 Meat Meat i-Pr Me i-Pr 770 Meat Meat i-Pr Meat Meat 771 Meat Meat i-Pr Meat i-Pr 772 Meat Meat i-Pr i-Pr i-Pr 773 Meat iPr Meat H Me 774 Meat iPr i-Pr H Me 775 Meat iPr i-Pr H Meat 776 Meat iPr i-Pr H i-Pr 777 Meat iPr i-Pr Me Me 778 Meat iPr i-Pr Me Meat 779 Meat iPr i-Pr Me i-Pr 780 Meat iPr i-Pr Meat Meat 781 Meat iPr i-Pr Meat iPr 782 Meat iPr i-Pr i-Pr i-Pr 783 i-Pr H H H H 784 i-Pr H H H Me 785 i-Pr H H H Meat 786 i-Pr H H H i-Pr 787 i-Pr H H Me Me 788 i-Pr H H Me Meat 789 i-Pr H H Me i-Pr 790 i-Pr H H Meat Meat i-Pr H H Meat i-Pr 791 i-Pr H H i-Pr i-Pr 792 i-Pr H Me H Me 793 i-Pr H Me H Meat 794 i-Pr H Me H i-Pr 795 i-Pr H Me Me Me 796 i-Pr H Me Me Meat 797 i-Pr H Me Me i-Pr 798 i-Pr H Me Meat Meat 799 i-Pr H Me Meat i-Pr 800 i-Pr H Me i-Pr i-Pr 801 i-Pr H Meat H Me 802 i-Pr H Meat H Meat 803 i-Pr H Meat H i-Pr 804 i-Pr H Meat Me Me 805 i-Pr H Meat Me Meat 806 i-Pr H Meat Me i-Pr 807 i-Pr H Meat Meat Meat 808 i-Pr H Meat Meat i-Pr 809 i-Pr H Meat i-Pr i-Pr 810 i-Pr H i-Pr H Me 811 i-Pr H i-Pr H Meat 812 i-Pr H i-Pr H i-Pr 813 i-Pr H i-Pr Me Me 814 i-Pr H i-Pr Me Meat 15 i-Pr H i-Pr Me i-Pr 816 i-Pr H i-Pr Meat Meat 817 i-Pr H i-Pr Meat i-Pr 818 i-Pr H i-Pr i-Pr i-Pr 819 i-Pr Me Me H Me 820 i-Pr Me Me H Meat 821 i-Pr Me Me H i-Pr 822 i-Pr Me Me Me Me 823 i-Pr Me Me Me Meat 824 i-Pr Me Me Me i-Pr 825 i-Pr Me Me Meat Meat 826 i-Pr Me Me Meat i-Pr 827 i-Pr Me Me i-Pr i-Pr 828 i-Pr Me Meat H Me 829 i-Pr Me Meat H Meat 830 i-Pr Me Meat H iPr 831 i-Pr Me Meat Me Me 832 i-Pr Me Meat Me Meat 833 i-Pr Me Meat Me i-Pr 834 i-Pr Me Meat Meat Meat 835 i-Pr Me Meat Meat i-Pr 836 i-Pr Me Meat i-Pr i-Pr 837 i-Pr Me i-Pr H Me 838 i-Pr Me i-Pr H Meat 839 i-Pr Me i-Pr H i-Pr 840 i-Pr Me i-Pr Me Me 841 i-Pr Me i-Pr Me Meat 842 i-Pr Me i-Pr Me i-Pr 843 i-Pr Me i-Pr Meat Meat 844 i-Pr Me i-Pr Meat i-Pr 845 i-Pr Me i-Pr i-Pr i-Pr 846 i-Pr Meat Meat H Me 847 i-Pr Meat Meat H Meat 848 i-Pr Meat Meat H i-Pr 849 i-Pr Meat Meat Me Me 850 i-Pr Meat Meat Me Meat 851 i-Pr Meat Meat Me i-Pr 852 i-Pr Meat Meat Meat Meat 853 i-Pr Meat Meat Meat i-Pr 854 i-Pr Meat Meat iPr i-Pr 855 i-Pr Meat i-Pr H Me 856 i-Pr Meat i-Pr H Meat 857 i-Pr Meat i-Pr H i-Pr 858 i-Pr Meat i-Pr Me Me 859 i-Pr Meat i-Pr Me Meat 860 i-Pr Meat i-Pr Me i-Pr 861 i-Pr Meat i-Pr Meat Meat 862 i-Pr Meat i-Pr Meat i-Pr 863 i-Pr Meat i-Pr i-Pr i-Pr 864 i-Pr iPr Meat H Me 865 i-Pr i-Pr i-Pr H Me 866 i-Pr i-Pr i-Pr H Meat 867 i-Pr i-Pr i-Pr H i-Pr 868 i-Pr i-Pr i-Pr Me Me 869 i-Pr i-Pr i-Pr Me Meat 870 i-Pr i-Pr i-Pr Me i-Pr 871 i-Pr i-Pr i-Pr Meat Meat 872 i-Pr i-Pr i-Pr Meat i-Pr 873 i-Pr i-Pr i-Pr i-Pr i-Pr

R ^{a is} -CO-NR ^b R ^c R ^a R ^b R ^c 874 H H Me 875 H H Meat 876 H H i-Pr 877 H Me Me 878 H Me Meat 879 H Me i-Pr 880 H Meat Meat 881 H Meat i-Pr 882 H i-Pr i-Pr 883 Me Me Me 884 Me Me Meat 885 Me Me i-Pr 886 Me Meat Meat 887 Me Meat i-Pr 889 Me i-Pr i-Pr 890 Me CF ₃ Me 891 Me CF ₃ Meat 892 Me CF ₃ i-Pr 893 Meat Me Me 894 Meat Me Meat 895 Meat Me iPr 896 Meat Meat Meat 897 Meat Meat i-Pr 898 Meat i-Pr i-Pr 899 Meat CF ₃ Me 900 Meat CF ₃ Meat 901 Meat CF ₃ i-Pr 902 i-Pr Me Me 903 i-Pr Me Meat 904 i-Pr Me i-Pr 905 i-Pr Meat Meat 906 i-Pr Meat i-Pr 907 i-Pr i-Pr i-Pr 908 i-Pr CF ₃ Me 909 i-Pr CF ₃ Meat 910 i-Pr CF ₃ i-Pr ₉₁₁ CF ₃ Me Me 912 CF ₃ Me Meat 913 CF ₃ Me i-Pr 914 CF ₃ Meat Meat 915 CF ₃ Meat i-Pr 916 CF ₃ i-Pr i-Pr 917 CF ₃ CF ₃ Me 918 CF ₃ CF ₃ Meat 919 CF ₃ CF ₃ i-Pr 920 H H Me 921 H H Meat 922 H H i-Pr 923 H Me Me 924 H Me Meat 925 H Me i-Pr 926 H Meat Meat 927 H Meat i-Pr 928 H i-Pr i-Pr 929 Me Me Me 930 Me Me Meat 931 Me Me i-Pr 932 Me Meat Meat 933 Me Meat i-Pr 934 Me i-Pr i-Pr 935 Me CF ₃ Me 936 Me CF ₃ Meat 937 Me CF ₃ i-Pr 938 Meat Me Me 939 Meat Me Meat 940 Meat Me iPr 941 Meat Meat Meat 942 Meat Meat i-Pr 943 Meat i-Pr i-Pr 944 Meat CF ₃ Me 945 Meat CF ₃ Meat 946 Meat CF ₃ i-Pr 947 i-Pr Me Me 948 i-Pr Me Meat 949 i-Pr Me i-Pr 950 i-Pr Meat Meat 951 i-Pr Meat i-Pr 952 i-Pr i-Pr i-Pr 953 i-Pr CF ₃ Me 954 i-Pr CF ₃ Meat 955 i-Pr CF ₃ i-Pr 956 CF ₃ Me Me 957 CF ₃ Me Meat 958 CF ₃ Me i-Pr 959 CF ₃ Meat Meat 960 CF ₃ Meat i-Pr 961 CF ₃ i-Pr i-Pr 962 CF ₃ CF ₃ Me 963 CF ₃ CF ₃ Meat 964 CF ₃ CF ₃ iPr 965 H H Me 966 H H Meat 967 H H i-Pr 968 H Me Me 969 H Me Meat 970 H Me i-Pr 971 H Meat Meat 972 H Meat i-Pr 973 H i-Pr i-Pr 974 Me Me Me 975 Me Me Meat 976 Me Me i-Pr 977 Me Meat Meat 978 Me Meat i-Pr 979 Me i-Pr i-Pr 980 Me CF ₃ Me 981 Me CF ₃ Meat 982 Me CF ₃ iPr 983 Meat Me Me 984 Meat Me Meat 985 Meat Me i-Pr 986 Meat Meat Meat 987 Meat Meat i-Pr 988 Meat i-Pr i-Pr 989 Meat CF ₃ Me 990 Meat CF ₃ Meat 991 Meat CF ₃ i-Pr 992 i-Pr Me Me 993 i-Pr Me Meat 994 i-Pr Me i-Pr 995 i-Pr Meat Meat 996 i-Pr Meat i-Pr 997 i-Pr i-Pr i-Pr 998 i-Pr CF ₃ Me 999 i-Pr CF ₃ Meat 1000 i-Pr CF ₃ i-Pr 1001 CF ₃ Me Me 1002 CF ₃ Me Meat 1003 CF ₃ Me i-Pr 1004 CF ₃ Meat Meat 1005 CF ₃ Meat i-Pr 1006 CF ₃ i-Pr i-Pr 1007 CF ₃ CF ₃ Me 1008 CF ₃ CF ₃ Meat 1009 CF ₃ CF ₃ i-Pr

R ^a -C = CR ^b -CH-R ^c R ^a Rb R ^c 1010 Me H Me 1011 Me H Meat 1012 Me H i-Pr 1013 Me H CF ₃ 1014 Meat H Me 1015 Meat H Meat 1016 Meat H i-Pr 1017 Meat H CF ₃ 1018 i-Pr H Me 1019 i-Pr H Meat 1020 i-Pr H i-Pr 1021 i-Pr H CF ₃ 1022 CF ₃ H Me 1023 CF ₃ H Meat 1024 CF ₃ H i-Pr 1025 CF ₃ H CF ₃

R ^a R ^b -N-CH 2 -CO-R ^c R ^d R ^a R ^b R ^c R ^d 1026 H Me H H 1027 H Me Me H 1028 H Me Meat H 1029 H Me i-Pr H 1030 H Me CF ₃ H 1031 H Me Me Me 1032 H Me Meat Me 1033 H Me i-Pr Me 1034 H Me CF ₃ Me 1035 H Me Meat Meat 1036 H Me i-Pr Meat 1037 H Me CF ₃ Meat 1038 H Me i-Pr iPr 1039 H Me CF ₃ iPr 1040 H Me CF ₃ CF ₃ 1041 H Meat H H 1042 H Meat Me H 1043 H Meat Meat H 1044 H Meat iPr H 1045 H Meat CF ₃ H 1046 H Meat Me Me 1047 H Meat Meat Me 1048 H Meat i-Pr Me 1049 H Meat CF ₃ Me 1050 H Meat Meat Meat 1051 H Meat iPr Meat 1052 H Meat CF ₃ Meat 1053 H Meat i-Pr i-Pr 1054 H Meat CF ₃ i-Pr 1055 H Meat CF ₃ CF ₃ 1056 H i-Pr H H 1057 H i-Pr Me H 1058 H i-Pr Meat H 1059 H i-Pr i-Pr H 1060 H i-Pr CF ₃ H 1061 H i-Pr Me Me 1062 H i-Pr Meat Me 1063 H i-Pr i-Pr Me 1064 H i-Pr CF ₃ Me 1065 H i-Pr Meat Meat 1066 H i-Pr i-Pr Meat 1067 H i-Pr CF ₃ Meat 1068 H i-Pr i-Pr i-Pr 1069 H i-Pr CF ₃ i-Pr 1070 H i-Pr CF ₃ CF ₃ 1071 Me Me H H 1072 Me Me Me H 1073 Me Me Meat H 1074 Me Me i-Pr H 1075 Me Me CF ₃ H 1076 Me Me Me Me 1077 Me Me Meat Me 1078 Me Me i-Pr Me 1079 Me Me CF ₃ Me 1080 Me Me Meat Meat 1081 Me Me iPr Meat 1082 Me Me CF ₃ Meat 1083 Me Me i-Pr i-Pr 1084 Me Me CF ₃ i-Pr 1085 Me Me CF ₃ CF ₃ 1086 Me Meat H H 1087 Me Meat Me H 1088 Me Meat Meat H 1089 Me Meat i-Pr H 1090 Me Meat CF ₃ H 1091 Me Meat Me Me 1092 Me Meat Meat Me 1093 Me Meat i-Pr Me 1094 Me Meat CF ₃ Me 1095 Me Meat Meat Meat 1096 Me Meat i-Pr Meat 1097 Me Meat CF ₃ Meat 1098 Me Meat i-Pr i-Pr 1099 Me Meat CF ₃ i-Pr 1100 Me Meat CF ₃ CF ₃ 1101 Me i-Pr H H 1102 Me i-Pr Me H 1103 Me i-Pr Meat H 1104 Me i-Pr i-Pr H 1105 Me i-Pr CF ₃ H 1106 Me i-Pr Me Me 1107 Me i-Pr Meat Me 1108 Me i-Pr i-Pr Me 1109 Me i-Pr CF ₃ Me 1110 Me i-Pr Meat Meat 1111 Me i-Pr i-Pr Meat 1112 Me i-Pr CF ₃ Meat 1113 Me i-Pr i-Pr i-Pr 1114 Me i-Pr CF ₃ i-Pr 1115 Me i-Pr CF ₃ CF ₃ 1116 Meat Meat H H 1117 Meat Meat Me H 1118 Meat Meat Meat H 1119 Meat Meat i-Pr H 1120 Meat Meat CF ₃ H 1121 Meat Meat Me Me 1122 Meat Meat Meat Me 1123 Meat Meat i-Pr Me 1124 Meat Meat CF ₃ Me 1125 Meat Meat Meat Meat 1126 Meat Meat i-Pr Meat 1127 Meat Meat CF ₃ Meat 1128 Meat Meat i-Pr i-Pr 1129 Meat Meat CF ₃ i-Pr 1130 Meat Meat CF ₃ CF ₃ 1131 Meat i-Pr H H 1132 Meat i-Pr Me H 1133 Meat i-Pr Meat H 1134 Meat i-Pr i-Pr H 1135 Meat i-Pr CF ₃ H 1136 Meat i-Pr Me Me 1137 Meat i-Pr Meat Me 1138 Meat i-Pr i-Pr Me 1139 Meat i-Pr CF ₃ Me 1140 Meat i-Pr Meat Meat 1141 Meat i-Pr i-Pr Meat 1142 Meat i-Pr CF ₃ Meat 1143 Meat i-Pr i-Pr i-Pr 1144 Meat i-Pr CF ₃ i-Pr 1145 Meat i-Pr CF ₃ CF ₃ 1146 i-Pr i-Pr H H 1147 i-Pr i-Pr Me H 1148 i-Pr i-Pr Meat H 1149 i-Pr i-Pr i-Pr H 1150 i-Pr i-Pr CF ₃ H 1151 i-Pr i-Pr Me Me 1152 i-Pr i-Pr Meat Me 1153 i-Pr i-Pr i-Pr Me 1154 i-Pr i-Pr CF ₃ Me 1155 i-Pr i-Pr Meat Meat 1156 i-Pr i-Pr i-Pr Meat 1157 i-Pr i-Pr CF ₃ Meat 1158 i-Pr i-Pr i-Pr i-Pr 1159 i-Pr i-Pr CF ₃ i-Pr 1160 i-Pr i-Pr CF ₃ CF ₃

<Example 2>: (t-Bu- N =) 2 W (Me-CO = CH-CMe = Ni-Pr) thin tungsten (W) using the _second expected that deposition of the film

(t-Bu-N =) ₂ W (Me-CO = CH-CMe = Ni-Pr) ₂ was synthesized as described in Example 1. One way to deposit these compounds and above all the tungsten film is described using the following examples, and it is expected that a tungsten (W) film will be obtained in this way.

The tungsten molecule will be placed in the canister. The vapor of (t-Bu-N =) ₂ W (Me-CO = CH-CMe = Ni-Pr) ₂ will be transferred to the reactor by flowing nitrogen into the heated canister to provide sufficient vapor. Hydrogen will be introduced into the deposition system to react with the tungsten vapor on the surface of the wafer in an ALD scheme (introduction of the precursor vapor separated by a sufficiently long inert gas purge). Any type of reducing agent may be selected, although hydrogen (H ₂ ) is considered to be the molecule to be selected. A tungsten (W) film will be obtained. The analysis results will show that a typical saturation mode in ALD mode is obtained when the time of introduction of the vapor of the tungsten molecule is prolonged.

The foregoing description is merely illustrative of the present invention, and various modifications may be made without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all techniques within the scope of the same should be construed as being included in the scope of the present invention.

Claims (19)

A tungsten precursor compound represented by the following formula (2)
(2)

(-XZY-) in Formula 2 is one of the ligands represented by the following Chemical Formulas 3, 4, 5, 7, 8, 9, 10,
[Chemical Formula 3]

[Chemical Formula 7]

[Chemical Formula 10] < EMI ID =

In Formulas 3, 4, 5, 7, 8, 9, 10, and 11,
R ^a , R ^b , R ^c , R ^d and R ^e are each independently H; C ₁ -C ₆ linear, branched, or cyclic alkyl groups; C ₁ -C ₆ linear, branched, or alkylsilyl groups, cyclic alkylsilyl groups (mono, bis, or trisalkyl); A C ₁ -C ₆ linear, branched, or cyclic fluoroalkyl group wherein some or all of the substituents are F; And an alkoxy group substituted with a C ₁ -C ₆ linear, branched or cyclic alkyl group, and n is an integer of 1 or 2.
delete delete The method of claim 1, wherein R ^a , R ^b , R ^c , R ^d , and R ^e are each independently a C ₁ -C ₆ linear, branched, cyclic alkyl group or a C ₁ -C ₆ linear, branched A tungsten precursor compound selected from a fluoroalkyl group 2. The method of claim 1, wherein ^{R a, R b, R c} , R d, R e is methyl, ethyl, isopropyl, each independently-tungsten precursor compound selected from methyl (CF ₃₎ with a profile, Access 2. The compound according to claim 1, wherein n is a tungsten precursor compound
A method of depositing a tungsten-containing film,
Introducing at least one tungsten precursor compound represented by the following formula into a reactor in which at least one substrate is disposed; And
Depositing at least a portion of the tungsten precursor compound on at least one substrate to form a tungsten containing film, wherein the tungsten precursor compound is a tungsten-containing film deposition process characterized by a compound represented by the following formula
(2)

(-XZY-) in Formula 2 is one of the ligands represented by the following Chemical Formulas 3, 4, 5, 7, 8, 9, 10,
[Chemical Formula 3]

[Chemical Formula 7]

[Chemical Formula 10] < EMI ID =

In Formulas 3, 4, 5, 7, 8, 9, 10, and 11,
R ^a , R ^b , R ^c , R ^d and R ^e are each independently H; C ₁ -C ₆ linear, branched, or cyclic alkyl groups; C ₁ -C ₆ linear, branched, or alkylsilyl groups, cyclic alkylsilyl groups (mono, bis, or trisalkyl); A C ₁ -C ₆ linear, branched, or cyclic fluoroalkyl group wherein some or all of the substituents are F; And an alkoxy group substituted with a C ₁ -C ₆ linear, branched or cyclic alkyl group, and n is an integer of 1 or 2. 8. The method of claim 7,
Introducing into the reactor additional one or more reactive gases, 9. The method of claim 8,
Characterized in that the reaction gas is a reducing agent or an oxidizing agent 10. The method of claim 9,
The reaction gas is NH ₃ , H ₂ , SiH ₄ ; Si ₂ H ₆ ; Si ₃ H ₈ ; NH ₃ ; (CH _{3) 2} SiH _2; (C ₂ H ₅ ) ₂ SiH ₂ ; (CH ₃₎ SiH _3; (C ₂ H ₅ ) SiH ₃ ; Phenylsilane; N ₂ H ₄ ; N (SiH _{3) 3;} N (CH ₃₎ H _{2; N (C 2 H 5) H} 2; N (CH _{3) 2} H; _{N (C 2 H 5) 2} H; N (CH _{3) 3; N (C 2 H 5) 3} ; (SiMe ₃ ) ₂ NH; (CH ₃₎ HNNH _2; (CH _{3) 2} NNH _2; Phenylhydrazine; B ₂ H ₆ ; 9-borabicyclo [3,3,1] nonane; Dihydrobenzene furan; Pyrazoline; Trimethyl aluminum; Dimethyl zinc; Diethylzinc; Its radical species; And mixtures thereof. &Lt; RTI ID = 0.0 &gt; 10. The method of claim 9,
The reaction gas may be an oxidizing agent such as O ₂ ; O ₃ ; H ₂ O; H ₂ O ₂ ; NO; NO ₂ ; N ₂ O; Carboxylic acid; Its radical species; And mixtures thereof. &Lt; RTI ID = 0.0 &gt; 10. The method of claim 9,
Characterized in that the tungsten precursor compound and the reactive gas are introduced into the reactor at substantially the same time, and the reactor is constituted by chemical vapor deposition 13. The method of claim 12,
Characterized in that the reactor is constituted by plasma enhanced chemical vapor deposition The method of claim 9, wherein the tungsten precursor compound and the reactive gas are introduced into the reactor at substantially the same time, and wherein the reactor is configured to deposit an atomic layer. 15. The method of claim 14,
Characterized in that the reactor is constituted by a plasma enhanced chemical vapor deposition
delete delete 8. The method of claim 7,
Wherein R ^a , R ^b , R ^c , R ^d and R ^e are each independently a tungsten precursor compound selected from methyl, ethyl, iso-propyl, 8. The method of claim 7,
Wherein n represents an integer of 2

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