Patent Grant
9085823
This application is a 371 of International PCT Application PCT/EP2009/059067, filed Jul. 15, 2009, the entire contents of which are incorporated herein by reference. This application further claims foreign priority to EP 08305444.5 filed Aug. 1, 2008, the entire contents of which are incorporated herein by reference.
The invention relates to a method for forming a tantalum-containing layer on a substrate using an ALD (Atomic Layer Deposition) process.
The continuous shrink of the critical sizes in modern Integrated Circuit (IC) features associated with 3D topology architectures offers highest density at the expense of process complexity.
According to the International Technology Roadmap for Semiconductors (ITRS), physical techniques commonly used in the semiconductor industry for the deposition of thin films are no more suitable to meet the requirements in the future technology node, notably for high aspect ratio structures. Techniques like PVD (Physical Vapor Deposition), i-PVD (ionized-Physical Vapor Deposition) or PECVD (Plasma-Enhanced Chemical Vapor Deposition), employing high energy particles, induce high sticking coefficient which leads to poor step coverage, especially along the sidewalls.
The main industrial options to enable the deposition of highly uniform and conformal thin films with reasonable throughput in high aspect ratio structures are techniques such as MOCVD (Metal-Organic Chemical Vapor Deposition) or ALD (Atomic Layer Deposition).
However, films deposited by MOCVD need high thermal budget and generally follow a 3D-growth mechanism described by a Volmer-Weber model. Thin films grow by clusters nucleation and such technique also leads to insufficient step coverage.
The typical ALD process (e.g. as described in RITALA M., LESKELA M., Atomic Layer Deposition, Handbook of thin films materials) involves gaseous reactants led onto a substrate by pulses, separated by inert gas purging. In MOCVD, gaseous reactants are injected simultaneously and react by thermal self-decomposition while in ALD; the loss of the ligand is thermally induced by reaction with the surface groups on the substrate. In a temperature range, the surface reactions are self-limited, which allow the deposition of highly uniform and conformal films. Precursors must be volatile and stable enough to be easily transferred to the reaction chamber without being decomposed. Moreover, they must be reactive enough with the chemical groups of the surface to ensure reasonable growth rate.
ALD is of particular interest for the deposition of group V (V, Nb, Ta) metal containing films. Interest for conductive group V (V, Nb, Ta) metal containing thin films deposited by ALD has risen in the past few years for several main applications such as: copper diffusion barrier in BEOL applications, CMOS metal gate, High-k layers in memory devices or electrodes for Metal-Insulator-Metal applications (DRAM . . . ).
However, common group V (V, Nb, Ta) based metal-organic precursors are not suitable for the deposition of conductive group V (V, Nb, Ta) containing films without assisting the thermal ALD process by plasma techniques.
Halides such as TaCl5 have been widely investigated such as disclosed in U.S. Pat. No. 6,268,288. However, some by-products generated during the deposition process, such as HCl or Cl2, can cause surface/interface roughness that can be detrimental to the final properties. Moreover, Cl or F impurities can be detrimental to the final electrical properties. It is therefore expected to find new compounds having sufficient volatility but without containing Cl, F, or Br atoms.
Alkylamides and alkylimides, such as Ta(NMe2)5 (PDMAT), Ta(=NtBu)(NEt2)3 (TBTDET), Ta(═NiPr)(NMe2)3 (IPTDMT), Ta(═NCH2C(CH3)3)(NEt2)3 (TAIMATA), Ta(═NiPr)(NEt2)3 (IPTDET) have been considered. Those precursors present the advantages of being frequently liquid at room temperature, like TBTDET, and having fair volatility, sufficient shelf-life and thermal stability. Urdahl & al, in WO02/20870, have also proposed TBTDET for the deposition of Ta2O5. TAIMATA has been disclosed in U.S. Pat. No. 6,593,484. A method for the deposition of tantalum nitride films by sequential injection of TBTDET or TAIMATA and other N source has been disclosed in US 2004/0219784. A method and apparatus of generating PDMAT precursor has been disclosed in US 2004/0014320.
In 2005, two Japanese patent applications JP 2005-132756 (A) and JP 2005-132757 disclosed the precursors mentioned above by introducing cyclopentadienyl based ligands, as described by the following general formulas:
R1 is an alkyl comprising 1 to 3 carbon atoms, and R2 is an alkyl comprising 1 to 5 carbon atoms, R3 is an alkyl comprising 1 to 6 carbon atoms, R4 is methyl or ethyl, m is an integer of 0 to 5 and, as for n, m+n becomes five or less, Z is chlorine, bromine, or iodine. However, using such metal-organic precursors as described by MOCVD at 600° C., can not be suitable for the deposition of highly uniform and conformal thin films. Such deposition will result in a poor step coverage in high aspect ratio structures.
Nevertheless, according to the state of the art, MOCVD process is the best solution in terms of interesting growth rate, so others processes have never been implemented.
According to the present invention, surprisingly, it appears that in applying Atomic Layer Deposition techniques to a molecule which could have been first proposed for Chemical Vapor Deposition solves the inconvenience mentioned above. Moreover, using these precursors based chemistry by ALD allows to deposit thin films more conductive than those obtained from the conventional TBTDET.
According to a first embodiment, the invention relates to a method for forming a tantalum-containing layer on a substrate, the method comprising at least the steps of:
a) providing a vapor comprising at least one precursor compound of the formula Cp(R1)mTa(NR22)2(═NR3) (I):
Wherein:
R1 is an organic ligand, each one independently selected in the group consisting of H, linear or branched hydrocarbyl radical comprising from 1 to 6 carbon atom;
R2 is an organic ligand, each one independently selected in the group consisting of H, linear or branched hydrocarbyl radical comprising from 1 to 6 carbon atom;
R3 is an organic ligand selected in the group consisting of H, linear or branched hydrocarbyl radical comprising from 1 to 6 carbon atom;
b) reacting the vapor comprising the at least one compound of formula (I) with the substrate, according to an atomic layer deposition process, to form a layer of a tantalum-containing complex on at least one surface of said substrate. Alternatively, R1 is an organic ligand, each one independently selected in the group consisting of H, linear or branched; alkyl, alkylsilyl, alkylamides, alkylsilylamides and/or alkoxides. R2 may be chosen between an alkyl, alkylsilyl, alkylamides, alkylsilylamides and/or alkoxides. R3 may be chosen between an alkyl, alkylsilyl, alkylamides, alkylsilylamides and/or alkoxides, preferably, R3 is an alkyl with 3 or 4 carbon atoms such as isopropyl or tert-butyl.
In a specific configuration, each R1 and R2 is different from one another, which can have beneficial features on the compound physical properties.
The inventors found that, surprisingly, imido ligands, ═NR, in an ALD process, can stabilize early transition metal in high-oxidation state by metal-nitrogen π-bonding and are playing a major role in the preservation of nitrogen atoms into the solid. They usually possess, as TBTDET or TAIMATA, very good thermal properties (good stability and volatility). The increase of the thermodynamic stability of the imido complexes compared to the amido ones allows depositing TaN thin films at higher temperatures and preventing a CVD like regime which destroys the self-limiting growth. So there is a synergy effect in using imido ligands, ═NR, with an ALD process.
Furthermore, other embodiments of the invention are:
The method according to the invention further comprising the step:
c) reaction of the complex formed obtained in step b) with a reagent selected from another metal source, reducing reactants and/or nitriding reactants and/or oxidizing reactants.
The method of the invention, wherein:
The method wherein the vapour provided in step a) further comprises one or more metal (M′)-organic precursor(s) to produce thin films containing tantalum and M′. M′ being independently selected from any other element in the group II, III-A, Sulpher (S), transition metal, lanthanoids, or rare-earth metals.
The method of the invention, wherein m=0 in the formula (I).
The method, further comprising providing at least one reaction gas wherein the at least one reaction gas is selected from the group consisting of hydrogen, hydrogen sulfide, hydrogen selenide, hydrogen telluride, carbon monoxide, ammonia, organic amine, silane, disilane, higher silanes, silylamines, diborane, hydrazine, methylhydrazine, chlorosilane and chloropolysilane, metal alkyl, arsine, phosphine, trialkylboron, oxygen, ozone, water, hydrogen peroxide, nitrous oxide, nitrogen monoxide, nitrogen dioxide, alcohols, plasma comprising fragments of those species, and combinations thereof, preferably ozone or water.
The method, wherein the tantalum precursor of formula (I) is selected in the group consisting of:
(Cp)Ta(=NtBu)(NEt2)2;
(Cp)Ta(=NtBu)(NMe2)2;
(Cp)Ta(═NC5H)(NMe2)2;
(Cp)Ta(=NtBu)(N(EtMe)2)2;
(Cp)Ta(═NiPr)(NEt2)2;
(Cp)Ta(═NiPr)(NMe2)2;
(MeCp)Ta(=NtBu)(NMe2)2;
(MeCp)Ta(═NiPr)(NMe2)2.
The method, wherein the temperature of the substrate is 25° C. to 450° C., preferably 380° C. to 425° C., and wherein the atomic layer deposition chamber containing the substrate has a pressure of 0.133 Pa to 133 kPa, preferably below 27 kPa.
The method, further comprising the step of purging excess vapor comprising the at least one compound of formula (I) from the substrate, with an inert gas selected from the group consisting of hydrogen, nitrogen, helium, argon, and mixtures thereof.
The method, wherein the tantalum-containing layer has a thickness of 0 μm to 10 μm.
A method of manufacturing a semiconductor structure, comprising the steps of the method defined in the present invention, wherein the substrate is a semiconductor substrate.
A New Technique to Deposit Tantalum Containing Films Using Metal-Organic Precursors Described by the Following General Formula Cp(R1)mTa (NR22)2(═NR3) as material source.
The vaporization of the tantalum source is realized by introducing a carrier gas into a heated container containing the said metal source. The container is preferably heated at a temperature allowing to get the said metal source at a sufficient vapor pressure. The carrier gas can be selected from Ar, He, H2, N2 or mixtures of them. The said tantalum source can be mixed to a solvent or to another metal source or to a mixture of them in the container. The container can for instance be heated at temperatures in the range of 25° C.-300° C., preferably below 150° C. Those skilled in the art will consider that the temperature of the container can be adjusted to control the amount of precursor vaporized. To control the evaporation level in the container, the pressure in the container can be modified. By reducing the pressure in the container, the level of vaporation of the tantalum source can be increased. The pressure in the container can for instance be changed in the range of 0.133 Pa until 133 kPa, preferably below 27 kPa.
The said tantalum source can also be fed in liquid state to a vaporizer where it is vaporized. The said metal source can be mixed to a solvent. The said tantalum source can be mixed to another metal source. The said mixture of metal sources can be mixed to a solvent or a mixture of solvent. The said tantalum source can be mixed to a stabilizer. The said solvent can be selected in the group consisting of alcanes such as hexane, heptane, octane, aromatic solvents such as benzene, toluene, mesitylene, xylene, silicon containing solvent such as hexamethyldisiloxane, hexamethyldisilazane, tetramethylsilane, sulphur containing solvents such as dimethylsulfoxide, oxygen containing solvent such as tetrahydrofuran, dioxane.
The said vaporized tantalum source is then introduced into a reaction chamber where it is contacted to the surface of a substrate. The substrate can be heated to sufficient temperature to obtain the desired film at sufficient growth rate and with desired physical state and composition. Typical temperatures range from 150° C. to 600° C. Preferably the temperature is lower or equal to 450° C. The process can be assisted by a plasma technique. The use of plasma techniques allows ionizing the precursor vapor and/or the reactant used to form radicals and thus improve the reactivity of the said vaporized metal source and/or the reactivity of other gaseous species, used in the process.
The method of the present invention is a method assisted or not by plasma techniques, for depositing a tantalum containing film on the surface of a substrate comprising at least: exposition of the surface of a substrate to a tantalum precursor described by the following general formula Cp(R1)mTa(NR22)2(═NR3) (I) and a reagent selected from reducing reactants, oxidizing reactants and/or nitriding reactants, to produce a tantalum containing thin film on the surface. Example of reagent can be selected in the list: H2, N2H2, methylhydrazine, NH3, SiH4, Si2H6, Si3H8, TSA, Si2Cl6 or any chlorosilane or chloropolysilane, trimethylaluminium, ZnEt2 or any metal alkyl, BH3, B2H6, PH3, AsH3, trimethylboron, triethylboron, CO, monoamines, diamines, mixtures of them or plasma comprising fragment of those species. Example of oxidizing reagents can be selected in the list: O2, O3, H2O, H2O2, NO, NO2, N2O, CH3OH or any alcohol, mixture of them or plasma comprising fragments of those species. Oxidizing species may alternatively be metal-organic compounds containing a metal-oxygen bond.
The deposition method, of this invention improves upon known methods by allowing the use of lower temperatures and producing higher quality films. Moreover, TaN ALD using TBTDET and NH3 resulted in thin films with resistivity values from 1.1 to 1.4 Ohmcm in the 240° C.-280° C. temperature range, while with the precursors of the invention the film resistivity is less than 0.5 Ohmcm and thus, two to three times lower compared to the conventional TBTDET. Furthermore, the thermal stability is improved: TBTDET is decomposed at 270° C., while TBTDETCp is decomposed from 315° C. The ALD process will be provided with a higher temperature.
Another advantage is that the growth rate reaches a good level with the process of the invention: 0.6 Angstrom·cycle−1.
In one embodiment, the method of the invention consists in introducing alternatively a tantalum-organic precursor described by the general formula (I) Cp(R1)mTa(NR22)2(═NR3) into a reaction chamber with a reagent. In a temperature range which depends on the precursor thermal stability and physical properties, the said tantalum-organic precursor reacts in a self-limited manner with the chemical bonds present onto the surface of a substrate, chosen without limitation. Preferably, un-deposited tantalum-organic precursors molecules are removed from the reaction chamber. The reagent introduced, reacts also in a self-limited manner.
Once all the complexes present on the surface of the substrate have reacted with the reagent, species are removed from the reaction chamber by a purge gas. The purge gas can for instance be selected within N2, Ar, He, H2 mixtures of them. The purge gas may additionally contain other gas species that do not modify the chemical reactivity of the surface. Alternatively, the purge can be realized by vacuum. This process can be repeated as many times as necessary to reach the desired film thickness. The reagent is selected from reducing reactants, nitriding reactants, oxidizing reactants, or a mixture of them.
Example of reagent can be selected in the list: H2, N2H2, methylhydrazine, NH3, SiH4, Si2H6, Si3H8, TSA, Si2Cl6 or any chlorosilane or chloropolysilane, trimethylaluminium, ZnEt2 or any metal alkyl, BH3, B2H6, PH3, AsH3, trimethylboron, triethylboron, CO, monoamines, diamines, mixtures of them or plasma comprising fragment of those species. Example of oxidizing reagents can be selected in the list: O2, O3, H2O, H2O2, NO, NO2, N2O, CH3OH or any alcohol, mixture of them or plasma comprising fragments of those species, preferably plasma comprising H2, NH3 or O2. Oxidizing species may alternatively be metal-organic compounds containing a metal-oxygen bond.
In one embodiment, the method of the invention consists in introducing alternatively first a tantalum-organic precursor described by the general formula (I) Cp(R1)mTa(NR22)2(═NR3) into a reaction chamber and second a reagent or another metal source. This another metal source being independently selected from any other element in the group II, III-A, III-B, Sulpher (S), transition metal, lanthanoids, or rare-earth metals. In a temperature range which depends on the precursor thermal stability and physical properties, the said metal-organic precursors react in a self-limited manner with the chemical bonds present onto the surface of a substrate. Preferably, un-deposited metal-organic precursors molecules are removed from the reaction chamber. The reagent introduced, reacts also in a self-limited manner. Once all the complexes present on the surface of the substrate have reacted with the reagent, species are removed from the reaction chamber by a purge gas. The purge gas can for instance be selected within N2, Ar, He, H2 mixtures of them. The purge gas may additionally contain other gas species that do not modify the chemical reactivity of the surface.
Alternatively, the purge can be realized by vacuum. This process can be repeated as many times as necessary to reach the desired film thickness. The reagent is selected without limitation from reducing reactants, nitriding reactants, oxidizing reactants, or a mixture of them. Example of reagent can be selected in the list: H2, N2H2, methylhydrazine, NH3, SiH4, Si2H6, Si3H8, TSA, Si2Cl6 or any chlorosilane or chloropolysilane, trimethylaluminium, ZnEt2 or any metal alkyl, BH3, B2H6, PH3, AsH3, trimethylboron, triethylboron, CO, monoamines, diamines, mixtures of them or plasma comprising fragment of those species. Example of oxidizing reagents can be selected in the list: O2, O3,
H2O, H2O2, NO, NO2, N2O, CH3OH or any alcohol, mixture of them or plasma comprising fragments of those species. Oxidizing species may alternatively be metal-organic compounds containing a metal-oxygen bond.
Examples of metal-organic precursors described by the general formula Cp(R1)mM(NR22)2(═NR3) which can be used in the present invention, include without limitation:
(Cp)Ta(=NtBu)(NEt2)2
(Cp)Ta(=NtBu)(NMe2)2
(Cp)Ta(═NC5H11)(NMe2)2
(Cp)Ta(=NtBu)(N(EtMe)2)2
(Cp)Ta(═NiPr)(NEt2)2
(Cp)Ta(═NiPr)(NMe2)2.
TaCp(=NtBu)(NEt2)2 is stored into a container. The container is heated at 120° C. and N2 is used as carrier gas at a flow of 50 sccm. Ammonia (NH3) is used as nitrogen source. The substrate is heated at 400° C. The precursor is sequentially introduced into the reaction chamber with NH3: during the first step a pulse of TaCp(=NtBu)(NEt2)2 is introduced during about 8 seconds, followed by a 13 seconds N2 purge. A pulse of NH3 is then introduced into the reaction chamber during 8 seconds, followed by a 13 seconds N2 purge. The first step is then done again. 400 cycles are performed this way. A film of tantalum nitride is obtained.
The results obtained in terms of growth rate for thin films deposited by ALD, in the 390° C. -450° C. temperature range, from (Cp)Ta(=NtBu)(NEt2)2 and ammonia are shown in
A step coverage of 100% is achieved for thin films deposited on substrates with 3D architectures. The bottoms such as the sidewalls are conformally and uniformly recovered.
Therefore, the method disclosed in the present invention allows to deposit tantalum carbo-nitride on structures with high aspect ratio, which was not possible with the same precursor by using conventional deposition technique.
TaCp(=NtBu)(NEt2)2 is stored into a container. The container is heated at 120° C. and N2 is used as carrier gas at a flow of 50 sccm. Ammonia (NH3) is used as nitrogen source. The substrate is heated at 400° C. The precursor is sequentially introduced into the reaction chamber with trimethyl aluminium (TMA) and NH3: during the first step a pulse of TaCp(=NtBu)(NEt2)2 is introduced during about 8 seconds, followed by a 13 seconds N2 purge. A pulse of trimethyl aluminium (TMA) is then introduced into the reaction chamber during about 8 seconds, followed by a 13 seconds N2 purge. A pulse of NH3 is then introduced into the reaction chamber during 8 seconds, followed by a 13 seconds N2 purge. The first step is then done again. 400 cycles are performed this way. A film of tantalum nitride is obtained.
TaCp(=NtBu)(NEt2)2 is stored into a container. The container is heated at 120° C. and N2 is used as carrier gas at a flow of 50 sccm. Ozone (O3) is used as oxygen source. The substrate is heated at 400° C. The precursor is sequentially introduced into the reaction chamber with O3: during the first step a pulse of TaCp(=NtBu)(NEt2)2 is introduced during about 8 seconds, followed by a 13 seconds N2 purge. A pulse of O3 is then introduced into the reaction chamber during 8 seconds, followed by a 13 seconds N2 purge. The first step is then done again. 400 cycles are performed this way. A film of tantalum oxy-nitride is obtained.
It will be understood that many additional changes in the details, materials, steps and arrangement of parts, which have been herein described in order to explain the nature of the invention, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims. Thus, the present invention is not intended to be limited to the specific embodiments in the examples given above.
| Number | Date | Country | Kind |
|---|---|---|---|
| 08305444 | Aug 2008 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2009/059067 | 7/15/2009 | WO | 00 | 5/4/2011 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2010/012595 | 2/4/2010 | WO | A |
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