JP2013530304A - Ruthenium-containing precursors for CVD and ALD - Google Patents

Abstract

Ruthenium-containing precursors and methods of using them in CVD and ALD are disclosed. The disclosed precursor is a general formula L _m Ru (CO) ₃ , wherein L is a linear or branched unsaturated hydrocarbon or a cyclic unsaturated hydrocarbon having two or more substituents. , M is 1 or 2).
[Selection] Figure 1

Description

  Ruthenium-containing precursors and methods of using them in CVD and ALD are disclosed.

[Cross-reference of related applications]
This application claims the benefit of US Provisional Patent Application No. 61 / 325,487, filed Apr. 19, 2010, the entire contents of which are hereby incorporated by reference. It claims the benefit of US Non-Provisional Application No. 12 / 981,798, filed December 30th.

Ruthenium films and ruthenium-containing films such as SrRuO and RuO ₂ are used in several components such as metal electrodes and Cu seed layers in semiconductor devices. The resistivity of ruthenium is lower than Ir and Pt. In addition, RuO ₂ has better conductivity than the two corresponding Ir and Pt metal oxides, which means that the deposited metal layer can be oxidised (eg, O ₂ , O ₃₎ during subsequent processing. ) Is important. The smaller the chip size, the thinner each layer must be. Therefore, chemical vapor deposition (CVD), preferably atomic layer deposition (ALD) techniques are desired, and precursors that can be used in CVD and ALD modes are also desired.

  A variety of ruthenium complexes are available, some being studied in CVD mode or ALD mode. However, such as deposition of films that mostly show low vapor pressure and / or high impurity content (usually C and O), long incubation times, low adhesion, and non-uniformity in deep trenches, etc. Have the disadvantages. In addition, some precursors are not liquid and need to be dissolved in a solvent or solvent mixture to allow easy delivery of vapor to the reaction chamber.

Tricarbonyl ruthenium products have been reported as CVD / ALD precursors (see, for example, US Pat. Patent Document _{4, (R n -CHD) Ru (} CO) 3 precursor (wherein, R represents C1~C4 straight or branched alkyl, alkylamides, alkoxides, alkylsilylamides, amidinates, carbonyl and And / or selected from the group consisting of fluoroalkyl substituents, n can be in the range of 1-8.

US Pat. No. 6,517,616 US Pat. No. 6,897,160 JP 2002-212112 A International Publication No. 2008/034468 Pamphlet

  There remains a need for ruthenium-containing precursors with properties suitable for vapor deposition.

<Notation and terminology>
Certain abbreviations, symbols and terms are used throughout the following specification and claims. For example, the term “unsaturated hydrocarbon” refers to an unsaturated functional group containing only carbon and hydrogen atoms. Furthermore, the term “unsaturated hydrocarbon” refers to a linear, branched or cyclic unsaturated hydrocarbon group. Examples of the linear unsaturated hydrocarbon group include, but are not limited to, an ethylene group, a propylene group, and a butene group. Examples of branched unsaturated hydrocarbon groups include, but are not limited to, 2-methyl-2,4-pentadiene. Examples of the cyclic unsaturated hydrocarbon group include, but are not limited to, a cyclohexadienyl group.

  The abbreviation “Me” refers to the methyl group, the abbreviation “Et” refers to the ethyl group, the abbreviation “Pr” refers to the propyl group, the abbreviation “iPr” refers to the isopropyl group, and the abbreviation “Bu” Refers to butyl (n-butyl), the abbreviation “tBu” refers to tert-butyl, the abbreviation “sBu” refers to sec-butyl, and the abbreviation “CHD” refers to cyclohexadienyl.

  Common abbreviations for elements from the Periodic Table of Elements are used herein. It should be understood that elements may be referred to by these abbreviations (eg, Ru refers to ruthenium, Sr refers to strontium, etc.).

A method for forming a ruthenium-containing layer on a substrate is disclosed. A reaction chamber is provided having at least one substrate disposed therein. Steam is introduced into the reaction chamber. The steam is represented by the formula [L] _m Ru (CO) ₃ (wherein L is a linear or branched unsaturated hydrocarbon, or a cyclic unsaturated hydrocarbon having two or more substituents, and m is At least one compound having 1 or 2). Vapor is brought into contact with the substrate to form a ruthenium containing layer using a deposition process on at least one surface of the substrate. The method can further include one or more of the following aspects:
The deposition process is CVD and / or ALD;
At least one compound is selected from the group consisting of Ru (ethylene) ₂ (CO) ₃ , Ru (propylene) ₂ (CO) ₃ , Ru (butene) ₂ (CO) ₃ ;
At least one compound is Ru (2,4-pentadiene) (CO) ₃ , Ru (2-methyl-2,4-pentadiene) (CO) ₃ , Ru (1,4-pentadiene) (CO) ₃ , Ru _{(2,4-hexadiene)} (CO) 3, Ru (2,4-hexamethylene diethyl _Nar) (CO) 3, Ru _{(2,4-heptadiene) (CO) 3, Ru (} 1,4- dimethyl-1, 3-cyclohexadiene) (CO) ₃ , Ru (1-methyl-4-ethyl-1,3-cyclohexadiene) (CO) ₃ , Ru (1-methyl-4-n-propyl-1,3-cyclohexadiene) ) (CO) ₃ , Ru (1-methyl-4-isopropyl-1,3-cyclohexadiene) (CO) ₃ , Ru (1,5-dimethyl-1,4-cyclohexadiene) (CO) ₃ , Ru ( 1-methyl-5 -Ethyl-1,4-cyclohexadiene) (CO) ₃ , Ru (1-methyl-5-n-propyl-1,4-cyclohexadiene) (CO) ₃ and Ru (1-methyl-5-isopropyl-1) , 4-cyclohexadiene) (CO) ₃ ;
L is “C═C—C═C” or “C═C—CH ₂ —C═C”;
At least one compound is liquid at a temperature in the range of approximately −20 ° C. to approximately 100 ° C .;
At least one compound is liquid at a temperature in the range of approximately −20 ° C. to approximately 30 ° C .;
At least one compound is liquid at a temperature in the range of approximately −20 ° C. to approximately 0 ° C .;
The deposition process is a thermal deposition process or a plasma deposition process;
The reaction chamber contains 1 to 200 wafers;
The deposition process is performed at about 0.01 Torr (1.33 Pa) to about 1000 Torr (13332).
In the pressure range of 2 Pa);
The deposition process is performed in a pressure range of about 0.1 Torr (13.3 Pa) to about 100 Torr (133332.2 Pa);
The deposition process is carried out in a temperature range of about 10 ° C. to about 400 ° C .;
The deposition process is carried out in a temperature range of about 25 ° C. to about 350 ° C .;
The deposition process is carried out in a temperature range of about 50 ° C. to about 300 ° C .;
Introducing reactants into the reaction chamber;
The reactant is selected from the group consisting of hydrogen (H ₂ ), ammonia (NH ₃ ), silane (SiH ₄ ), diethylsilane (SiEt ₂ H ₂ ), their excited species, and mixtures thereof;
The reactant is from the group consisting of oxygen (O ₂ ), water (H ₂ O), ozone (O ₃ ), H ₂ O ₂ , NO, NO ₂ , carboxylic acid (RCOOH), their excited species, and mixtures thereof. Selected.

  For a further understanding of the nature and objects of the invention, reference should be made to the following detailed description taken together with the accompanying figures.

It is a graph of thermogravimetric analysis (TGA) which shows the mass-loss rate with respect to temperature about Ru (1-methyl-4- isopropyl- 1, _3- cyclohexadiene) (CO) ₃ . 2 is a graph of vapor pressure versus temperature for Ru (1-methyl-4-isopropyl-1,3-cyclohexadiene) (CO) ₃ .

  A ruthenium-containing precursor is disclosed. The disclosed precursors can be thermally stable (at delivery conditions) so as to be used with high reactivity for CVD and ALD deposition.

The disclosed precursor is a general formula L _m Ru (CO) ₃ , wherein L is a linear or branched unsaturated hydrocarbon or a cyclic unsaturated hydrocarbon having two or more substituents. , M is 1 or 2).

In one embodiment, the disclosed precursor has the formula L ₂ Ru (CO) ₃ and L is a linear unsaturated hydrocarbon such as ethylene, propylene or butene. Exemplary precursors include Ru (ethylene) ₂ (CO) ₃ , Ru (propylene) ₂ (CO) ₃ and Ru (butene) ₂ (CO) ₃ .

In an alternative embodiment, the disclosed precursor has the formula LRu (CO) ₃ and L is attached to the Ru atom as shown below:

In this embodiment, L is 2,4-pentadiene, 2-methyl-2,4-pentadiene, 1,4-pentadiene, 2,4-hexadiene, 2,4-hexadienal, 2,4-heptadiene. obtain. Alternatively, L is a cyclohexadiene molecule having two or more substituents, such as 1,4-dimethyl-1,3-cyclohexadiene, 1-methyl-4-ethyl-1,3-cyclohexadiene, 1- Methyl-4-n-propyl-1,3-cyclohexadiene, 1-methyl-4-isopropyl-1,3-cyclohexadiene, 1-methyl-5-methyl-1,4-cyclohexadiene, 1-methyl-5 -Ethyl-1,4-cyclohexadiene, 1-methyl-5-n-propyl-1,4-cyclohexadiene, 1-methyl-5-isopropyl-1,4-cyclohexadiene. Exemplary precursors include Ru (2,4-pentadiene) (CO) ₃ , Ru (2-methyl-2,4-pentadiene) (CO) ₃ , Ru (1,4-pentadiene) (CO) ₃ , Ru _{(2,4-hexadiene) (CO) 3, Ru (} 2,4- hexamethylene diethyl _{Nar) (CO) 3, Ru (} 2,4- _{heptadiene) (CO) 3, Ru (} 1,4- dimethyl - 1,3-cyclohexadiene) (CO) ₃ , Ru (1-methyl-4-ethyl-1,3-cyclohexadiene) (CO) ₃ , Ru (1-methyl-4-n-propyl-1,3- Cyclohexadiene) (CO) ₃ , Ru (1-methyl-4-isopropyl-1,3-cyclohexadiene) (CO) ₃ , Ru (1,5-dimethyl-1,4-cyclohexadiene) (CO) ₃ , Ru (1-methyl-5- Ethyl-1,4-cyclohexadiene) (CO) ₃ and Ru (1-methyl-5-n-propyl-1,4-cyclohexadiene) (CO) ₃ . Preferably, the precursor is Ru (1-methyl-4-isopropyl-1,3-cyclohexadiene) (CO) ₃ .

  The disclosed precursor is liquid at a temperature in the range of about −20 ° C. to about 100 ° C., more preferably about −20 ° C. to about 30 ° C., and even more preferably about −20 ° C. to about 0 ° C. preferable.

<Selection of ligand>
Some L _m Ru (CO) ₃ compounds exhibit suitable properties for CVD / ALD deposition. The selection of the L ligand can be performed based on the purpose of use of the obtained ruthenium-containing layer. However, the oxidation state of the ruthenium atom and the steric hindrance of the ligand L are not always the same, and some structures cannot be made.

For example, if L is not a neutral ligand (eg, substituted cyclopentadiene), the ruthenium oxidation state in the L _m Ru (CO) ₃ compound is not zero, which results in a stable L _m Ru (CO) ₃ compound. can get. In such cases, oxygen is required during the CVD or ALD process to break the bond between the Ru atom and the non-neutral L ligand. As a result, the resulting ruthenium-containing layer can also contain oxygen.

However, when L is a neutral ligand (eg, diene (m = 1) or unsaturated hydrocarbon (m = 1 or 2)), the oxidation state of ruthenium in the L _m Ru (CO) ₃ compound is zero. It is. In that situation, no oxygen or ozone would be required to break the bond. In some cases, hydrogen can be used instead of oxygen. The resulting Ru-containing layer can be applied to some parts that cannot use oxygen, such as a barrier layer.

<Active site>
In addition to the selection of ligands as described above, some ligands cannot make L _m Ru (CO) ₃ structures. The ligand molecule L is “C (1) = C (2) -C (3) = C (4)” or “C (5) = C (6) -C (7) H ₂ -C (8)”. = C (9) ". In the case of a diene molecule, the two double bonds should be closer, and C (2), C (3), C (6), C (8) have a substituent on the carbon (other than hydrogen). Should not. In other words, 1,3-diene molecules are preferred over 1,4-diene molecules.

In addition, C (2), C ( 3), C (6) or C (8) optional non-hydrogen substituents on the carbon molecules _may interfere with L m M _{(CO) 3} formation of the molecule. To avoid steric hindrance, the ligand molecule may require an “open site” that results in a tbp (trigonal bipyramidal) structure. For example, L
When the ligand does not have an active site, such as when 1-methyl-4-isopropyl-1,4-cyclohexadiene or 1,3,5-trimethyl-1,4-cyclohexadiene, LM ( No CO) ₃ product was obtained.

<Deposition method>
The disclosed precursors can be used to form a ruthenium-containing layer on one or more substrates (eg, a semiconductor substrate or substrate assembly) using a deposition process. This method may be useful in the manufacture of semiconductor devices, photovoltaic devices, LCD-TFT devices and flat panel devices. The method includes providing a substrate, preparing a vapor containing at least one ruthenium-containing precursor, and contacting the vapor containing the ruthenium-containing precursor with the substrate (usually sending the vapor to the substrate). And supplying a reducing or oxidizing agent vapor to the substrate to form a ruthenium-containing layer on at least one surface of the substrate.

  The disclosed precursor compounds can be deposited using any deposition method known to those skilled in the art to form ruthenium-containing films. Examples of suitable deposition methods include conventional chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), low pressure chemical vapor deposition (LPCVD), atomic layer deposition (ALD), pulsed chemical vapor deposition (P-CVD), plasma enhanced. These include, but are not limited to, atomic layer deposition (PE-ALD), combinations thereof, and / or any other deposition technique known to those skilled in the art. Preferably, the deposition method is a thermal evaporation process or a plasma evaporation process. More preferably, the deposition method is ALD or PE-ALD.

  Precursor vapor is introduced into a reaction chamber containing at least one substrate. The reaction chamber may contain 1 to 200 wafers. The reaction chamber can be any enclosure or chamber of the device in which the deposition process takes place, such as, but not limited to, a parallel plate reactor, a cold wall reactor, a hot wall reactor, a single wafer reaction. Reactor, multi-wafer reactor, or other type of deposition system.

  The temperature and pressure within the reaction chamber and the temperature of the substrate are maintained at suitable conditions such that contact of the ruthenium-containing precursor vapor with the substrate results in the formation of a Ru-containing layer on at least one surface of the substrate. The Reactants may be used to help form the Ru-containing layer.

  The reaction chamber is in the range of about 0.01 Torr (1.33 Pa) to about 1000 Torr (133322 Pa), more preferably in the range of about 0.1 Torr (13.3 Pa) to about 100 Torr (133332.2 Pa). It can be maintained at pressure. The temperature in the reaction chamber can range from about 10 ° C to about 100 ° C, preferably from about 25 ° C to about 350 ° C, more preferably from about 50 ° C to about 300 ° C. One skilled in the art will recognize that the temperature can be optimized with a few experiments to achieve the desired result.

The type of substrate on which the ruthenium containing film is deposited depends on the end use. In some embodiments, the substrate is an oxide (eg, RuO ₂ based material, ternary oxide based material, etc.) used as a dielectric material in MIM technology, DRAM technology, FeRam technology, or as a gate dielectric in CMOS technology. Or a nitride-based film (eg, RuN) used as an oxygen barrier between the copper and the low-k layer. Other substrates can be used in the manufacture of semiconductor devices, photovoltaic devices, LCD-TFT devices or flat panel devices. Examples of such substrates include solid substrates such as metal substrates (for example, metal silicides such as Au, Pd, Rh, Ru, W, Al, Ni, Ti, Co, Pt, and TiSi ₂ , CoSi _2, and NiSi ₂ ). Metal nitride-containing substrates (eg TaN, TiN, TiAlN, WN, TaCN, TiCN, TaSiN and TiSiN), semiconductor materials (eg Si, SiGe, GaAs, InP, diamond, GaN and SiC), insulators (eg SiO ₂₎ ,
Other substrates comprising Si ₃ N ₄ , SiON, HfO ₂ , Ta ₂ O ₅ , ZrO ₂ , TiO ₂ , Al ₂ O ₃ and barium strontium titanate), or any combination of these materials, It is not limited to. The actual substrate utilized may also depend on the particular precursor embodiment utilized. However, in many cases, the preferred substrate utilized is selected from TiN type, Ru type and Si type substrates.

  The substrate may be heated to a temperature sufficient to obtain the desired ruthenium film or ruthenium-containing film at a sufficient growth rate and in the desired physical state and composition. Non-limiting examples of the temperature range in which the substrate can be heated include 150 ° C. to 600 ° C. Preferably, the temperature of the substrate is kept at 450 ° C. or lower.

  The precursor may be sent to the evaporator in a liquid state where it is evaporated prior to introduction into the reaction chamber. The precursor can optionally be mixed with one or more solvents, one or more metal sources, and a mixture of one or more solvents and one or more metal sources prior to evaporation. The solvent can be selected from the group consisting of toluene, ethylbenzene, xylene, mesitylene, decane, dodecane, octane, hexane, pentane and the like. The resulting concentration can range from approximately 0.05M to approximately 2M. The metal source can include any metal precursor currently known or later developed.

Alternatively, the precursor may be evaporated by passing the carrier gas through a container containing the precursor or by blowing the carrier gas into the precursor. The carrier gas and precursor are then introduced into the reaction chamber as vapor. The carrier gas, Ar, the He, N _2, and mixtures can be mentioned, but not limited to. The precursor can optionally be mixed with a solvent, another metal precursor, or a mixture thereof in the container. If desired, the vessel may be heated to a temperature that allows the precursor to be in a liquid phase and have sufficient vapor pressure. The container may be maintained at a temperature in the range of 0 ° C to 150 ° C, for example. One skilled in the art will recognize that the temperature of the vessel can be adjusted in a known manner to control the amount of precursor evaporated.

In addition to optionally mixing the solvent, metal precursor and stabilizer prior to introducing the precursor into the reaction chamber, the precursor may be mixed with the reactants in the reaction chamber. Exemplary reactant, _{H 2,} the hydrogen-containing liquid, alcohol (ROH (R is C1~C6 alkyl)), metal precursor, for example strontium-containing precursor, a barium-containing precursor, an aluminum-containing such as TMA Examples include, but are not limited to, precursors, and any combination thereof.

Without limitation, when the desired ruthenium-containing film also contains oxygen, such as RuO ₂ , the reactants are O ₂ , O ₃ , H ₂ O, H ₂ O ₂ , acetic acid, formalin, para It may include an oxygen source selected from, but not limited to, formaldehyde, and combinations thereof.

If the desired ruthenium-containing film also contains nitrogen, such as but not limited to ruthenium nitride, the reactants are nitrogen (N ₂ ), ammonia and its alkyl derivatives, imine, hydrazine and its alkyl derivatives, N-containing radicals (e.g. ^{_{N ·, NH ·, NH 2}} ·), nO, N 2 O, nO 2, amines, and are selected from any combination thereof, may include a nitrogen source which is not limited thereto.

If the desired ruthenium-containing film also contains carbon, such as but not limited to ruthenium carbide, the reactants are methane, ethane, propane, butane, ethylene, propylene, t-butylene, isobutylene, CCl ₄ , And any combination thereof, may include, but is not limited to, a carbon source.

If the desired ruthenium-containing film also contains silicon, such as, but not limited to, ruthenium silicide or ruthenium silicate, the reactants may be SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , TriDMAS. , BDMAS, BDEAS, TDEAS, TDMAS, TEMAS, (SiH ₃ ) ₃ N, (SiH ₃ ) ₂ O, trisilylamine, disiloxane, trisilylamine, disilane, trisilane, alkoxysilane SiH _x (OR ¹ ) _{4− x} , silanol Si (OH) _x (OR ¹ ) _4-x (preferably Si (OH) (OR ¹ ) ₃ , more preferably Si (OH) (OtBu) ₃ ), aminosilane SiH _x (NR ¹ R ² ) _4-x (where x is 1, 2, 3 or 4 and R ¹ and R ² are each independently H or linear A branched or cyclic C1-C6 carbon chain; preferably TriDMAS, BTBAS and / or BDEAS), and any combination thereof, may include, but is not limited to, a silicon source. The film of interest may alternatively contain germanium (Ge), in which case the Si-containing reactant described above can be replaced with a Ge-containing reactant.

The desired ruthenium-containing film is another metal, such as but not limited to B, In, Zn, Au, Pd, Ag, Ti, Ta, Hf, Zr, Nb, Mg, Al, Sr, Y, Ba, Ca , As, Sb, Bi, Sn, Pb, or combinations thereof, the reactant may include a second precursor containing a metal. The second precursor is B ₂ H ₆ , SbR ^{i ′} ₃ or SnR ^{i ′} ₄ (where R ^{i ′} is independently H, or a linear, branched or cyclic C1-C6 carbon chain. A metal alkyl such as Sb (OR ⁱ ) ₃ or Sn (OR ⁱ ) _4, where R ⁱ is each independently H, or a linear, branched or cyclic C1-C6 carbon chain. And metal alkoxides such as Sb (NR < ¹ > R < ² >) (NR < ³ > R < ⁴ >) (NR < ⁵ > R < ⁶ >) or Ge (NR < ¹ > R < ² >) (NR < ³ > R < ⁴ >) (NR < ⁵ > R < ⁶ >) (NR < ⁷ >). R ⁸ ) (where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently H, a C1-C6 carbon chain or a trialkylsilyl group; The carbon chain and the trialkylsilyl group are each linear, branched or cyclic) Beauty can be selected from any combination thereof, but is not limited thereto.

In one preferred embodiment, the reactants can be selected from hydrogen (H ₂ ), ammonia (NH ₃ ), silane (SiH ₄ ), diethylsilane (SiEt ₂ H ₂ ), excited species thereof, and mixtures thereof. However, it is not limited to these. In another preferred embodiment, the reactants are oxygen (O ₂ ), water (H ₂ O), ozone (O ₃ ), H ₂ O ₂ , NO, NO ₂ , carboxylic acid (RCOOH), their excited species, And mixtures thereof, but not limited thereto.

  The precursor and one or more reactants can be introduced into the reaction chamber simultaneously (chemical vapor deposition), sequentially (atomic layer deposition), or in other combinations. For example, the precursor can be introduced in one pulse and two additional metal sources can be introduced together in separate pulses (modified atomic layer deposition). Alternatively, the reaction chamber may already contain the reactants prior to introduction of the precursor. The reactants may pass through a plasma system located remotely from the reaction chamber and decompose into radicals. Alternatively, the precursor may be continuously introduced into the reaction chamber (pulse chemical vapor deposition) while introducing other metal sources by pulses. In each instance, the pulse can be followed by a purge or evacuation step that removes excess components introduced. In each example, the pulse lasts for a period ranging from about 0.01 seconds to about 10 seconds, alternatively from about 0.3 seconds to about 3 seconds, alternatively from about 0.5 seconds to about 2 seconds. Can be made.

In one non-limiting example of an atomic layer deposition type process, a gas phase of the disclosed precursor is introduced into a reaction chamber where it is contacted with a suitable substrate. Excess precursor can then be removed from the reaction chamber by purging and / or evacuating the reactor. An oxygen source is introduced into the reaction chamber where it reacts with the absorbed precursors in a self-limiting manner. Any excess oxygen source is removed from the reaction chamber by purging and / or evacuating the reaction chamber. If the desired film is a ruthenium oxide film, this two-step process can be used to obtain the desired film thickness, or this can be repeated until a film having the required thickness is obtained.

  Alternatively, if the desired film is a ruthenium metal oxide film, the metal precursor vapor can be introduced into the reaction chamber after the two-step process described above. The metal precursor is selected based on the nature of the ruthenium metal oxide being deposited. After introduction into the reaction chamber, the metal precursor is brought into contact with the substrate. Any excess metal precursor is removed from the reaction chamber by purging and / or evacuating the reaction chamber. Again, an oxygen source may be introduced into the reaction chamber to react with the second metal precursor. Excess oxygen source is removed from the reaction chamber by purging and / or evacuating the reaction chamber. After the desired film thickness is achieved, the process can be terminated. However, if a thicker film is desired, the entire four step process may be repeated. By alternately supplying the precursor, the metal precursor and the oxygen source, a film having a desired composition and thickness can be deposited.

Ruthenium-containing film or ruthenium-containing layer obtained by processes discussed above may include SrRuO and RuO _2. One skilled in the art will recognize that the desired film composition can be obtained by judicious selection of appropriate precursors and reactants.

  The following non-limiting examples are presented to further illustrate embodiments of the present invention. However, the examples are not intended to be exhaustive and are not intended to limit the scope of the invention described herein.

<Synthesis of Ru (1-methyl-4-isopropyl-1,3-cyclohexadiene) (CO) ₃ >
Ru ₃ (CO) ₁₂ (10 g, 15.6 mmol) was mixed with 1-methyl-4-isopropyl-1,3-cyclohexadiene (25 ml, 0.15 mol) in 200 ml of toluene at reflux for 17 hours. After the reaction, excess solvent and ligand molecules were removed under vacuum pressure. The remaining liquid was distilled twice under vacuum pressure to give a light yellow liquid as final product at 70 ° C./20 mmHg (yield approximately 82%). As another purification method, the products were separated by column chromatography (silica gel, solvent: hexane). The pale yellow fraction (Rf = 0.7) was collected and the solvent was removed at room temperature under vacuum pressure.

FIG. 1 is a thermogravimetric analysis (TGA) graph showing the mass loss rate versus temperature for Ru (1-methyl-4-isopropyl-1,3-cyclohexadiene) (CO) ₃ . TGA results show good evaporation without residue at 20 Torr.

FIG. 2 is a graph of vapor pressure versus temperature for Ru (1-methyl-4-isopropyl-1,3-cyclohexadiene) (CO) ₃ . In Vp = 16.624 to 5672.8 / T, ΔH = 47 kJ / mol.

  Many further changes in the details, materials, processes, and arrangements of members described and illustrated herein to illustrate the nature of the present invention will be described in the appended claims. It is understood that those skilled in the art can do within the principles and scope. Accordingly, the present invention is not intended to be limited to the specific embodiments in the examples and / or the accompanying drawings listed above.

Claims (13)

A method of forming a ruthenium-containing layer on a substrate,
a) providing a reaction chamber having at least one substrate disposed therein;
b) In the reaction chamber, the formula [L] _m Ru (CO) ₃ (wherein L is a linear or branched unsaturated hydrocarbon or a cyclic unsaturated hydrocarbon having two or more substituents) Introducing a vapor comprising at least one compound having: m is 1 or 2.
c) contacting the vapor with the substrate to form a ruthenium-containing layer using a deposition process on at least one surface of the substrate; contacting the vapor with the substrate;
Forming a ruthenium-containing layer on the substrate.   The method of claim 1, wherein the deposition process is CVD and / or ALD. The at least one compound is selected from the group consisting of Ru (ethylene) ₂ (CO) ₃ , Ru (propylene) ₂ (CO) ₃ , Ru (butene) ₂ (CO) _3. The method described. The at least one compound is Ru (2,4-pentadiene) (CO) ₃ , Ru (2-methyl-2,4-pentadiene) (CO) ₃ , Ru (1,4-pentadiene) (CO) ₃ , ru _{(2,4-hexadiene) (CO) 3, Ru (} 2,4- hexamethylene diethyl _{Nar) (CO) 3, Ru (} 2,4- _{heptadiene) (CO) 3, Ru (} 1,4- dimethyl -1 , 3-cyclohexadiene) (CO) ₃ , Ru (1-methyl-4-ethyl-1,3-cyclohexadiene) (CO) ₃ , Ru (1-methyl-4-n-propyl-1,3-cyclo Hexadiene) (CO) ₃ , Ru (1-methyl-4-isopropyl-1,3-cyclohexadiene) (CO) ₃ , Ru (1,5-dimethyl-1,4-cyclohexadiene) (CO) ₃ , Ru (1-methyl -5-ethyl-1,4-cyclohexadiene) (CO) ₃ , Ru (1-methyl-5-n-propyl-1,4-cyclohexadiene) (CO) ₃ and Ru (1-methyl-5-isopropyl) _{3. A process according} to claim 1 or 2 selected from the group consisting of -1,4-cyclohexadiene) (CO) ₃ . The method according to claim 1, wherein L is “C═C—C═C” or “C═C—CH ₂ —C═C”.   The said at least one compound is a liquid at a temperature in the range of about -20 ° C to about 100 ° C, preferably about -20 ° C to about 30 ° C, more preferably about -20 ° C to about 0 ° C. Or the method of 2.   The method of claim 2, wherein the deposition process is a thermal deposition process or a plasma deposition process.   The method according to claim 1 or 2, wherein the reaction chamber contains 1 to 200 wafers.   The deposition process is performed in a pressure range of about 0.01 Torr (1.33 Pa) to about 1000 Torr (133322 Pa), preferably about 0.1 Torr (13.3 Pa) to about 100 Torr (133332.2 Pa). The method according to claim 1 or 2.   The method of claim 1, wherein the vapor deposition process is performed in a temperature range of about 10 ° C. to about 400 ° C., preferably about 25 ° C. to about 350 ° C., more preferably about 50 ° C. to about 300 ° C.   The method of claim 1, further comprising introducing a reactant into the reaction chamber. The reactant hydrogen _(H 2), ammonia _(NH 3), silane _(SiH 4), diethyl silane (SiEt ₂ H _2), these excited species, and is selected from the group consisting of a mixture thereof, according to claim 11 The method described in 1. The reactant is a group consisting of oxygen (O ₂ ), water (H ₂ O), ozone (O ₃ ), H ₂ O ₂ , NO, NO ₂ , carboxylic acid (RCOOH), excited species thereof, and a mixture thereof. The method of claim 11, selected from:

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