Patent Grant
8476467
The present invention relates to organometallic precursors for use in chemical phase deposition processes such as chemical vapor deposition (CVD) or atomic layer deposition (ALD).
Various organometallic precursors are used to form high-κ dielectric thin metal films for use in the semiconductor industry. Various deposition processes are used to form metal-containing films, such as chemical vapor deposition (“CVD”) or atomic layer deposition (“ALD”), also known at atomic layer epitaxy. Organometallic precursors deposited by such chemical phase deposition processes have applications in nanotechnology and fabrication of semiconductor devices such as capacitor electrodes, gate electrodes, adhesive diffusion barriers and integrated circuits.
CVD is a chemical process whereby precursors are deposited on a substrate to form a solid thin film. In a typical CVD process, the precursors are passed over a substrate (wafer) within a low pressure or ambient pressure reaction chamber. The precursors react and/or decompose on the substrate surface creating a thin film of the desired material. Volatile byproducts are removed by gas flow through the reaction chamber. The deposition film thickness can be difficult to control because it depends on coordination of many parameters such as temperature, pressure, gas flow volumes and uniformity, chemical depletion effects and time.
ALD is a chemical process similar to CVD, except the ALD process separates the precursors during the reaction. The first precursor is passed over the substrate producing a monolayer on the substrate. Any excess unreacted precursor is pumped out of the reaction chamber. A second precursor is then passed over the substrate and reacts with the first precursor, forming a monolayer of film on the substrate surface. This cycle is repeated to create a film of desired thickness. ALD film growth is self-limited and based on surface reactions, creating uniform depositions that can be controlled at the nanometer scale.
Moss J., Mol. Catal. A: Chem., 107:169-174 (1996) reports an investigation and characterization of metal alkyl complexes of the type RMn(CO)5 (R=alkyl group) and CpM(CO)2R (Cp=η5-C5H5, M=Fe, Ru or Os), and binuclear complexes Cp(CO)2Ru(CH2)2Ru(CO)2Cp.
Current precursors for use in chemical phase deposition display low volatility, poor growth control and an inability to scale up. Therefore, there is a need for improved chemical phase deposition precursors, particularly for use in ALD and CVD, which display higher thermal stability, better adhesion, higher vapor pressure and carbon free layers.
There is now provided an organometallic precursor corresponding in structure to Formula I:
Cp(R)nM(CO)2(X) (Formula I)
wherein:
Other embodiments, including particular aspects of the embodiments summarized above, will be evident from the detailed description that follows.
In various aspects of the invention, organometallic precursors are provided which are useful in chemical phase deposition processes, particularly CVD and ALD, to form thin metal-containing films, such as metal or metal oxide films.
The methods of the invention are used to create, grow or form thin metal-containing films which display high dielectric constants. A dielectric thin film as used herein refers to a thin film having a high permittivity.
As used herein, the term “precursor” refers to an organometallic molecule, complex and/or compound which is delivered to a substrate for deposition to form a thin film by a chemical deposition process, such as chemical vapor deposition or atomic layer deposition.
In a particular embodiment, the precursor may be dissolved in an appropriate hydrocarbon or amine solvent. Appropriate hydrocarbon solvents include, but are not limited to aliphatic hydrocarbons, such as hexane, heptane and nonane; aromatic hydrocarbons, such as toluene and xylene; aliphatic and cyclic ethers, such as diglyme, triglyme and tetraglyme. Examples of appropriate amine solvents include, without limitation, octylamine and N,N-dimethyldodecylamine. For example, the precursor may be dissolved in toluene to yield a 0.05 to 1M solution.
The term “Cp” refers to a cyclopentadienyl (C5H5) ligand which is bound to a transitional metal. As used herein, all five carbon atoms of the Cp ligand are bound to the metal center in η5-coordination by π bonding, therefore the precursors of the invention are π complexes.
The term “alkyl” refers to a saturated hydrocarbon chain of 1 to 10 carbon atoms in length, such as, but not limited to, methyl, ethyl, propyl and butyl. The alkyl group may be straight-chain or branched-chain. For example, as used herein, propyl encompasses both n-propyl and iso-propyl; butyl encompasses n-butyl, sec-butyl, iso-butyl and tert-butyl. Further, as used herein, “Me” refers to methyl, and “Et” refers to ethyl.
The organometallic precursors of the invention have at least one metallic center comprising a transition metal (“M”). Examples of transition metals for use in the invention include, but are not limited to Sc, Y, La, Ti, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ni, Pd, Pt, Cu, Ag and Au. In particular, there is one metal center and M is Ru, Os or Fe. In a further particular embodiment, M is Ru.
Therefore, in one embodiment an organometallic precursor is provided which corresponds in structure to Formula I:
Cp(R)nM(CO)2(X) (Formula I)
wherein:
In one aspect of the embodiment, the precursor corresponds in structure to Formula I wherein:
In another aspect of the embodiment, the precursor corresponds in structure to Formula I wherein:
In another aspect of the embodiment, the precursor corresponds in structure to Formula I wherein:
In another aspect of the embodiment, the precursor corresponds in structure to Formula I, wherein:
In another aspect of the embodiment, the precursor corresponds in structure to Formula I, wherein:
In another aspect of the embodiment, the precursor corresponds in structure to Formula I, wherein:
In another aspect of the embodiment, the precursor corresponds in structure to Formula I, wherein:
In particular, the precursor corresponding in structure to Formula I, is selected from the group consisting of:
It has been discovered that substitution of the Cp ring and tailoring of the alkyl group bonded to the metal has shown useful properties for chemical phase deposition processes such as CVD or ALD, or a hybrid of CVD and ALD. Examples of such useful properties include higher vapor pressure (as demonstrated in
Therefore, in yet another embodiment, a method of forming a metal-containing thin film by ALD is provided. The method comprises delivering at least one precursor to a substrate, wherein the precursor corresponds in structure to Formula II:
Cp(R)nM(CO)2(X) (Formula II)
wherein:
And in another embodiment, a method of forming a metal-containing thin film by CVD is provided. The method comprises delivering at least one precursor to a substrate, wherein the precursor corresponds in structure to Formula II above.
In a particular embodiment, the precursor corresponds in structure to Formula II wherein:
In a particular embodiment, the precursor corresponds in structure to Formula II wherein:
In a particular embodiment, the precursor corresponds in structure to Formula II wherein:
In a particular embodiment, the precursor corresponds in structure to Formula II wherein:
In a particular embodiment, the precursor corresponds in structure to Formula II wherein:
In a particular embodiment, the precursor corresponds in structure to Formula II wherein:
In a particular embodiment of the invention, the precursor according to Formula II is selected from the group consisting of:
In a further particular embodiment, the precursor according to Formula II is selected from the group consisting of:
In a further particular embodiment, the precursor corresponding in structure to Formula II is (cyclopentadienyl)ruthenium(ethyl)(dicarbonyl).
In another embodiment, the precursor corresponds in structure to Formula I and/or II, wherein butyl is selected from the group consisting of n-butyl, sec-butyl, iso-butyl and tert-butyl.
In another embodiment, the precursor corresponds in structure to Formula I and/or II, wherein propyl is selected from the group consisting of n-propyl and iso-propyl.
The chemical phase deposition processes of the invention, such as ALD and CVD, can be used to form various metal-containing thin films, such as metal or metal oxide films, on substrates using at least one of the organometallic precursors according to Formula II. The film can be formed by the organometallic precursor independently or in combination with a co-reactant (can be referred to as co-precursor). Examples of such co-reactants include, but are not limited to hydrogen, hydrogen plasma, oxygen, air, water, ammonia, hydrazine, allylhydrazine, borane, silane, ozone or any combination thereof.
In one embodiment, the at least one precursor is delivered to the substrate in pulses alternating with pulses of an oxygen source to create a metal oxide film. Examples of such oxygen sources include, without limitation, H2O, O2 or ozone.
A variety of substrates can be used in the methods of the present invention. For example, the precursors according to Formula I and/or II may be delivered for deposition on substrates such as, but not limited to, silicon, silicon oxide, silicon nitride, tantalum, tantalum nitride, or copper.
The ALD and CVD methods of the invention encompass various types of ALD and CVD processes such as, but not limited to, conventional processes, liquid injection processes and photo-assisted processes.
In one embodiment, conventional CVD is used to form a metal-containing thin film using at least one precursor according to Formula I and/or II. For conventional CVD processes, see for example Smith, Donald (1995). Thin-Film Deposition: Principles and Practice. McGraw-Hill.
In another embodiment, liquid injection CVD is used to form a metal-containing thin film using at least one precursor according to Formula I and/or II.
Examples of liquid injection CVD growth conditions include, but are not limited to:
In another embodiment, photo-assisted CVD is used to form a metal-containing thin film using at least one precursor according to Formula I and/or II.
In a further embodiment, conventional ALD is used to form a metal-containing thin film using at least one precursor according to Formula I and/or II. For conventional and/or pulsed injection ALD process see for example, George S. M., et. al. J. Phys. Chem. 1996. 100:13121-13131.
In another embodiment, liquid injection ALD is used form a metal-containing thin film using at least one precursor according to Formula I and/or II, wherein at least one liquid precursor is delivered to the reaction chamber by direct liquid injection as opposed to vapor draw by a bubbler. For liquid injection ALD process see, for example, Potter R. J., et. al. Chem. Vap. Deposition. 2005. 11(3):159.
Examples of liquid injection ALD growth conditions include, but are not limited to:
In another embodiment, photo-assisted ALD is used to form a metal-containing thin film using at least one precursor according to Formula I and/or II. For photo-assisted ALD processes see, for example, U.S. Pat. No. 4,581,249.
Thus, the organometallic precursors, according to Formula I or II, utilized in these methods may be liquid, solid, or gaseous.
Ruthenium precursors of Formula I and/or II can be made by the following method:
reacting Ru3(CO)12 with 3(CpRn)H to yield 3Ru(CpRn)(CO)2H and 6CO;
reacting 2Ru(Cp)Rn(CO)2H with [O] to yield Ru2(CpRn)2(CO)4 and H2;
reacting Ru2(CpRn)2(CO)4 and 2NaK to yield 2K[Ru(CpRn)(CO)2]; and
reacting K[Ru(CpRn)(CO)2] and XBr to yield Cp(R)nRu(CO)2(X);
wherein:
X is C1-C10-alkyl;
R is C1-C10-alkyl;
and n is 0, 1, 2, 3, 4 or 5.
Alternatively, ruthenium precursors of Formula I and/or II can be made by the following method:
reacting Ru3(CO)12 with 3(CpRn)H to yield 3Ru(CpRn)(CO)2H and 6CO;
reacting Ru(CpRn)(CO)2H with BuLi to yield Li[Ru(CpRn)(CO)2] and BuH;
reacting Li[Ru(CpRn)(CO)2] with XBr to yield Ru(CpRn)(CO)2X and LiBr;
wherein:
X is C1-C10-alkyl;
R is C1-C10-alkyl;
and n is 0, 1, 2, 3, 4 or 5.
The precursors and methods disclosed herein are useful in semiconductor devices and are useful for computer memory and logic applications, such as dynamic random access memory (DRAM) and complementary metal oxide semi-conductor (CMOS) circuitry. They are useful in many applications such as capacitor electrodes, gate electrodes and as adhesive diffusion barrier metal.
Precursors contemplated by the invention include, but are not limited to those listed below. It will be noted that when n is zero, there is no R substituent and the cyclopentadienyl ligand is therefore unsubstituted. Further, the R substituent is σ-bonded and its depiction below represents that the cyclopentadienyl ligand may be substituted zero to five times.
The following examples are merely illustrative, and do not limit this disclosure in any way.
The synthesis of Ru(η5-CpMe)(CO)2Me [also referred to herein as (methylcyclopentadienyl)ruthenium(methyl)(dicarbonyl)] is demonstrated by the following two-step process.
Ru3(CO)12 (15.0 g, 23.5 mmols) was reacted with CpMeH in the normal manner except that solution was heated for 1.5 hours instead of 1.0 hour and reaction with oxygenated heptane for 2.5 hours rather than 2.0 hours. After cooling overnight, orange crystalline material (12.1 g, 73%) was obtained. The solution is reduced to 100 ml and a further (1.9 g, 11%) darker, crystalline material was obtained after standing overnight. Total yield 84%.
IR (hexane) 2007 m, 1968 m, 1960 s, 1940 m, 1788 s cm−1; (CH2Cl2) 1997 s, 1953 s, 1767 s cm−1.
NMR (C6D6) 1H δ 4.75 (m, 4H, CH), 4.54 (m, 4H, CH), 1.70 (s, 6H, CH3); 13C{1H} δ 221.7 (CO), 109.2 (C), 89.4 (CMe), 88.5 (CMe), 12.6 (Me).
Next, Ru2(η5-CpMe)2(CO)4 (20.4 g, 43.2 mmols) was dissolved in degassed THF (˜250 ml), the solution degassed again and NaK (7 ml) was added. Solution was stirred for 5-6 hours until sample quenched in MeI showed a complete reaction (2018, 1959 cm−1). Unlike Ru2(η5-Cp)2(CO)4 reaction, the quenched solution was pale yellow and the reduced solution was quite dark. There was no obvious precipitate. Solution makes up to ˜700 ml. Solution filtered into MeI (20 ml) with occasional shaking. Solvent was removed on rotavap (˜70 mm Hg) to give an oil which was dissolved in hexane (˜150 ml). Following filtration, solvent was removed on the rotavap, the oil was transferred to a small flask and the residual hexane was removed at 0.5 mm Hg to give 22 g of a dark red oil. Distillation was performed twice at 58-60° C. (0.5 mm Hg) to give a pale yellow mobile oil (17.1 g, 79) of (η5-CpMe)Ru(Me)(CO)2 depicted below.
A synthesis scheme to prepare CpRu(Et)(CO)2 [also referred to herein as (cyclopentadienyl)ruthenium(ethyl)(dicarbonyl) and depicted below] is demonstrated below.
Ru3(CO)12+3CpH→3Ru(Cp)(CO)2H+6CO
2Ru(Cp)(CO)2H+[O]→Ru2(Cp)2(CO)4+H2
Ru2(Cp)2(CO)4+2NaK→2K[Ru(Cp)(CO)2]
K[Ru(Cp)(CO)2]+EtBr→Ru(Cp)(CO)2Et+KBr
A further synthesis scheme and a method to prepare CpRu(Et)(CO)2 is demonstrated below.
Ru3(CO)12+3CpH→3Ru(Cp)(CO)2H+6CO
Ru(Cp)(CO)2H+BuLi→Li[Ru(Cp)(CO)2]+BuH
Li[Ru(Cp)(CO)2]+EtBr→Ru(Cp)(CO)2Et+LiBr
All handling was under inert conditions. A suspension of Ru3(CO)12 (10.0 g, 15.6 mmol) in dry, degassed heptane (400 ml) and cracked cyclopentadiene (20.5 g, 310 mmol) was refluxed for 1 hour. The volume was reduced to 60 ml by distilling the solvent and unreacted cyclopentandiene in a stream of nitrogen and cooled. Dry degassed pentane (100 ml) was added followed by the dropwise addition of a hexane solution of 1.6 M BuLi in hexane (31 ml, 50 mmol). The solution was stirred for 1 hour and dry, degassed ethyl bromide (10.9 g 100 mmol) added dropwise. The mixture was stirred for a further 2 hours, filtered and the solvent removed in vacuo. The product was distilled up a short Vigreux column at 56° at 0.2 mmHg (9.4 g, 80%).
1H-NMR (400 MHz, CDCl3) ppm 5.23 (s, 5H, Cp), 1.77 (q, 2H, J=7.5 Hz, CH2) ppm 1.37 (t, 1H, J=7.5 Hz, CH3)
13C{1H} NMR 202.4 (CO), 88.6 (Cp), 24.2 (CH2), 10.0 (CH3)
ν(CO) (hexane) 2020, 1960 cm−1
ALD growth using CpRuMe(CO)2 [also referred to herein as (cyclopentadienyl)ruthenium(methyl)(dicarbonyl)] and depicted below is demonstrated by the following example.
Ruthenium thin films were deposited in a custom-built ALD reactor. Cyclopentadienyl ruthenium(methyl)dicarbonyl (CpRuMe(CO)2) and air were used as precursors. The ruthenium films were deposited on silicon wafer substrates. Prior to deposition, the wafer substrates were dipped in a 10% HF:water mixture for 30 seconds. The growth temperature was 300° C. The growth pressure is 250 milliTorr. The reactor is continuously purged with 30 sccm of dry nitrogen. All the computer controlled valves in the reactor were the air operated ALD VCR valves from Cajon.
The amount of injected air was the volume trapped between the VCR gasket (a blank gasket with a 30 micron pin hole in it) and the ALD valve stem. For air at atmospheric pressure and temperature, this means that approximately 29 μmoles of air is pulsed into the reactor during the air injection cycle. The pulse length of the air precursor is approximately 1 second followed by a 2-5 second purge. No ruthenium was deposited when the air inject line was plugged.
The ruthenium was stored in a stainless steel ampoule. Attached directly to the ampoule was an air operated ALD valve. The output of this ALD valve was Tee'd with another ALD valve used for nitrogen injection. The Tee outlet leg was connected to a 500 cm3 stainless steel reservoir. The outlet of the reservoir was attached to a third ALD valve, called the inject valve, whose outlet goes directly to the reactor. Nitrogen injection was used to build up the total pressure behind the ruthenium inject valve so that the pressure was higher than the reactor growth pressure. The injected nitrogen was accomplished using a 30 micron pin hole VCR gasket as described above for air injection. All of the valves and ampoule were placed into an oven-like enclosure that allowed the ampoule, valves, and tubing to be heated uniformly to 50° C. to 120° C.
During the ALD growth operation, the valves were sequenced in the following manner. Immediately after an air injection, the ruthenium ampoule ALD valve and the nitrogen inject ALD valve were both opened. The nitrogen inject valve was closed after 0.2 seconds. The ruthenium vapors and injected nitrogen were allowed to equilibrate in the 500 cm3 reservoir during the air purge time (typically 2-5 seconds). After the air purge time had elapsed, the ruthenium ampoule ALD valve was closed, and after a 0.2 second wait time, the ruthenium inject valve was opened for 0.2 seconds. The ruthenium was allowed to purge from the reactor for typically 5 seconds. The air was then injected to start the ALD cycle all over again.
The effect of the dose of ruthenium precursor was investigated by varying the precursor temperature from 85° C. to 110° C. The growth at 85° C. is non-uniform. The growth with precursor temperature between 90° C. to 110° C. is uniform. Normal growth temperature is usually 90° C.
The total amount of cycles was 300. Results show that the deposition rate was independent of the ruthenium dose as varied through its vapor pressure, which in turn is varied through its evaporation temperature. This proves that the film growth proceeds in a self-limiting manner as is characteristic of ALD.
The films produce a featureless scanning electron micrograph as shown in
ALD growth using CpRuMe(CO)2 was also performed as in Example 4, except using an argon purge, as opposed to nitrogen, a ruthenium pulse length of 1 second, an air pulse length of 1 second.
ALD growth using CpRuEt(CO)2 [also referred to herein as (cyclopentadienyl)ruthenium(ethyl)(dicarbonyl)] and depicted below is demonstrated by the following example.
Ruthenium thin films were deposited in a custom-built ALD reactor. Cyclopentadienyl ruthenium(ethyl)dicarbonyl (CpRuEt(CO)2) and air was used as precursors. The ruthenium films were deposited on silicon wafer substrates. Prior to deposition, the wafer substrates were dipped in a 10% HF:water mixture for 30 seconds. The growth temperature was 265° C. The growth pressure was 100 milliTorr. The reactor was continuously purged with 10 sccm of argon. All the computer controlled valves in the reactor are the air operated ALD VCR valves from Cajon.
The amount of injected air was the volume trapped between the VCR gasket (a blank gasket with a 30 micron pin hole in it) and the ALD valve stein. For air at atmospheric pressure and temperature, this means that approximately 29 μmoles of air is pulsed into the reactor during the air injection cycle. The pulse length of the air precursor is approximately 2 seconds followed by a 2-5 second purge. No ruthenium was deposited when the air inject line was plugged.
The ruthenium was stored in a stainless steel ampoule. Attached directly to the ampoule was an air operated ALD valve. The output of this ALD valve was Tee'd with another ALD valve used for argon injection. The Tee outlet leg was connected to a 500 cm3 stainless steel reservoir. The outlet of the reservoir was attached to a third ALD valve, called the inject valve, whose outlet goes directly to the reactor. Argon injection was used to build up the total pressure behind the ruthenium inject valve so that the pressure is higher than the reactor growth pressure. The injected argon was accomplished using a 30 micron pin hole VCR gasket as described above for air injection. All of the valves and ampoule were placed into an oven-like enclosure that allowed the ampoule, valves, and tubing to be heated uniformly to 50° C. to 120° C.
During the ALD growth operation, the valves were sequenced in the following manner. Immediately after an air injection, the ruthenium ampoule ALD valve and the argon inject ALD valve were both opened. The argon inject valve was closed after 0.2 seconds. The ruthenium vapors and injected argon were allowed to equilibrate in the 500 cm3 reservoir during the air purge time (typically 2-5 seconds). After the air purge time had elapsed, the ruthenium ampoule ALD valve was closed, and after a 0.2 second wait time, the ruthenium inject valve was opened for 2 seconds. The ruthenium was allowed to purge from the reactor for typically 5 seconds. The air was then injected to start the ALD cycle all over again.
The effect of the dose of ruthenium precursor was investigated by varying the precursor temperature from 85° C. to 110° C. The growth at 85° C. is non-uniform. The growth with precursor temperature between 90° C. to 110° C. is uniform. Normal growth temperature is usually 90° C.
The total amount of cycles was 300. Results show that the deposition rate is independent of the ruthenium dose as varied through its vapor pressure, which in turn is varied through its evaporation temperature. This proves that the film growth proceeds in a self-limiting manner as is characteristic of ALD.
The process of Example 6 was repeated using the various substrates and cycles listed in the table below. Good growth was seen on metal substrates throughout an 800 cycle run.
All patents and publications cited herein are incorporated by reference into this application in their entirety.
The words “comprise”, “comprises”, and “comprising” are to be interpreted inclusively rather than exclusively.
This patent claims priority to U.S. provisional patent application Ser. No. 60/951,601 filed on 24 Jul. 2007. This application contains subject matter that is related to U.S. provisional patent application Ser. No. 60/951,628, co-filed on 24 Jul. 2007. The disclosure of each of the applications identified in this paragraph is incorporated herein by reference in its entirety.
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| Number | Date | Country | |
|---|---|---|---|
| 20100256406 A1 | Oct 2010 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60951601 | Jul 2007 | US |
