Methods and systems for forming metal-niobium oxide films

Abstract

A process of depositing a metal-niobium oxide film on a substrate using a deposition method may include a plurality of complete deposition cycles. Each complete deposition cycle may include performing a metal-oxidant sub-cycle and then performing a niobium sub-cycle. The metal-oxidant sub-cycle may include contacting the substrate with a metal precursor and a first oxygen precursor. The niobium subcycling may include contacting the substrate with at least a niobium precursor.

Description

Technical Field

[0001] This disclosure generally relates to the field of semiconductor device manufacturing, such as the manufacturing of capacitors in back-end processes (BEOL) and dynamic random access memory (DRAM), and more specifically, to the deposition of metal-niobium oxide films used as dielectric layers in capacitors. Background Technology

[0002] DRAM, BEOL, and other memory and / or logic devices utilize capacitors to store information bits. Such capacitors are formed by placing a dielectric material between two electrodes made of conductive material. As device size and spacing decrease, DRAM and BEOL devices typically use metal-insulator-metal (MIM) capacitors, where the electrode material is a highly conductive metal to ensure fast device speeds and store the same amount of charge in a reduced size. However, such MIM capacitors can be severely affected by high leakage currents. Reducing leakage current in MIM capacitors becomes a key aspect of achieving high capacitance density by shrinking the size of the insulating or dielectric layer of the MIM capacitor. Furthermore, three-dimensional (3D) DRAM and / or BEOL devices will ultimately require MIM capacitors that include dielectric layers with a dielectric constant greater than 50, or maintain at least 100 nF / cm² even as the size of the dielectric layer decreases. 2 MIM capacitors with high capacitance density are needed. Current dielectric materials used in MIM capacitors do not possess such high dielectric constants. Furthermore, some dielectric materials with high dielectric constants may suffer from high leakage currents. Therefore, there is a need for improved MIM capacitors with dielectric layers having dielectric constants greater than 50 and low leakage currents. In addition, innovative manufacturing technologies are required that can produce such dielectric layers with high dielectric constants and low leakage currents while meeting stringent thermal budgets and remaining cost-effective for high-volume production. Summary of the Invention

[0003] This summary is provided to present the chosen concepts in a simplified form. These concepts are further described in detail in the following description of exemplary embodiments of this disclosure. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0004] According to various embodiments, this document discloses a method for fabricating a niobium oxide-containing film, which can be used as a dielectric layer in a MIM capacitor. This niobium oxide-containing film can have a dielectric constant greater than 50 and low leakage current. The method for fabricating the niobium oxide-containing film may include multiple complete deposition cycles. Each of the multiple complete deposition cycles may include performing a metal-oxidant sub-cycle, followed by a niobium sub-cycle. Performing the metal-oxidant sub-cycle may include contacting the substrate with a metal precursor and a first oxygen precursor, while performing the niobium sub-cycle may include contacting the substrate with a niobium precursor.

[0005] In various embodiments, performing a niobium sub-cycle may further include contacting the substrate with a niobium precursor and a first oxygen precursor. Alternatively or additionally, in other embodiments, performing a niobium sub-cycle may further include contacting the substrate with a niobium precursor and a second oxygen precursor different from the first oxygen precursor.

[0006] In various embodiments, performing a niobium sub-cycle may further include supplying a first oxygen precursor to the reaction chamber after completing multiple full deposition cycles. Alternatively or additionally, in other embodiments, performing a niobium sub-cycle may further include supplying a second oxygen precursor to the reaction chamber after completing multiple full deposition cycles, wherein the second oxygen precursor is different from the first oxygen precursor.

[0007] In various embodiments, the method of fabricating a niobium oxide-containing film may further include removing excess precursors and reaction byproducts from the reaction chamber after contacting the substrate with the metal precursor, the first oxygen precursor, or the niobium precursor. In various embodiments, the method of fabricating a niobium oxide-containing film may further include maintaining the deposition temperature of the reaction chamber below 450°C.

[0008] In various embodiments, the metal precursor may include an alkali metal, alkaline earth metal, transition metal, rare earth metal, lanthanide metal, or post-transition metal. In some embodiments, the metal precursor includes bismuth, tantalum, or titanium. In some embodiments, the niobium oxide-containing film may include a dielectric constant between 30 and 250.

[0009] In various embodiments, the niobium oxide-containing film may include bismuth niobium oxide, and the metal precursor may include a bismuth precursor that includes at least a cyclopentadienyl ligand, an amide ligand, an imine ligand, an amidine ligand, a halide ligand, an alkyl ligand, an alkoxide ligand, a diketone ligand, or a diazabutadiene ligand.

[0010] In various embodiments, the niobium oxide-containing film may include titanium niobium oxide, and the metal precursor may include a titanium precursor, which includes at least a cyclopentadienyl ligand, an amide ligand, an imine ligand, an amidine ligand, a halide ligand, an alkyl ligand, an alkoxide ligand, a diketone ligand, or a diazabutadiene ligand.

[0011] In various embodiments, the niobium oxide-containing film may include niobium tantalum oxide, and the metal precursor may include a tantalum precursor that includes at least a cyclopentadienyl ligand, an amide ligand, an imine ligand, an amidine ligand, a halide ligand, an alkyl ligand, an alkoxide ligand, a diketone ligand, or a diazabutadiene ligand.

[0012] In various embodiments, the first oxygen precursor and / or the second oxygen precursor may include one or more of molecular oxygen, ozone, hydrogen peroxide, water, formic acid, nitrous oxide, nitrogen oxides, or nitrogen pentoxide.

[0013] In various embodiments, the niobium precursor may include at least a cyclopentadienyl ligand, an amide ligand, an imino ligand, an amidine ligand, a halide ligand, an alkyl ligand, an alkoxide ligand, a diketone ligand, or a diazabutadiene ligand.

[0014] According to various embodiments, a reactor system for fabricating a niobium oxide-containing film is disclosed herein. The reactor system may include a reaction chamber for supporting a substrate, a metal source connected to the reaction chamber and configured to provide a metal precursor, a niobium source connected to the reaction chamber and configured to provide a niobium precursor, a first oxygen source connected to the reaction chamber and configured to provide a first oxygen precursor, and / or a control system configured to control the reactor to perform multiple complete deposition cycles to deposit a niobium oxide-containing film on the substrate. Each complete deposition cycle may include a metal-oxidant sub-cycle, wherein the metal precursor may be supplied from the metal source to the reaction chamber, and the first oxygen precursor may be supplied from the first oxygen source to the reaction chamber. Each complete deposition cycle may also include a niobium sub-cycle, wherein a niobium precursor from the niobium source may be supplied to the reaction chamber.

[0015] In some embodiments, the niobium subcycle may further include supplying the reaction chamber with a niobium precursor from a niobium source and a first oxygen precursor from a first oxygen source. In some embodiments, the reactor system may further include a second oxygen source connected to the reaction chamber and configured to provide a second oxygen precursor different from the first oxygen precursor, and the niobium subcycle may further include supplying the reaction chamber with a niobium precursor from a niobium source and a second oxygen precursor from the second oxygen source.

[0016] In some embodiments, the control system of the reactor system may be further configured to control the reactor system to supply a first oxygen precursor from a first oxygen source to the reaction chamber after multiple complete deposition cycles have been completed. In other embodiments, the control system may be further configured to control the reactor to supply a second oxygen precursor from a second oxygen source to the reaction chamber after multiple complete deposition cycles have been completed.

[0017] All these embodiments are intended to fall within the scope of this disclosure. These and other embodiments will become apparent to those skilled in the art from the following detailed description of certain embodiments with reference to the accompanying drawings, and this disclosure is not limited to any particular embodiment discussed. Attached Figure Description

[0018] Although this specification concludes with claims that are specifically pointed out and clearly claimed as embodiments of this disclosure, the advantages of embodiments of this disclosure can be more readily determined from the description of certain examples of embodiments when read in conjunction with the accompanying drawings. Elements having the same element numbers in all the drawings are intended to be identical.

[0019] Figure 1 A reactor system according to an exemplary embodiment of the present disclosure is shown.

[0020] Figure 2 An exemplary process flow is shown, illustrating an entire cyclic deposition process for forming a metal-niobium oxide film according to an exemplary embodiment of the present disclosure.

[0021] Figure 3 Another exemplary process flow is shown, illustrating an entire cyclic deposition process for forming a metal-niobium oxide film according to an exemplary embodiment of the present disclosure.

[0022] Figure 4A and Figure 4B The experimental current-voltage (IV) characteristics and dielectric constant of bismuth oxide tantalum niobium films are shown.

[0023] Figure 5 A flowchart illustrating a method for manufacturing or fabricating a MIM capacitor having a metal-niobium oxide dielectric layer according to exemplary embodiments of the present disclosure is shown.

[0024] Figure 6A and Figure 6B Exemplary embodiments according to this disclosure are shown (e.g., using...) Figure 5 Simplified cross-sectional views of portions of two example MIM capacitors manufactured using the method described above.

[0025] It should be understood that the elements in the accompanying drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements in the drawings may be exaggerated relative to other elements to help improve the understanding of the embodiments illustrated in this disclosure. Detailed Implementation

[0026] Although certain embodiments and examples are disclosed below, those skilled in the art will understand that this disclosure extends beyond the specific disclosed embodiments and / or the uses of this disclosure and their obvious modifications and equivalents. Therefore, it is intended that the scope of this disclosure should not be limited to the specific embodiments described herein. The illustrations presented herein are not intended to be actual views of any particular material, apparatus, structure, or device, but are merely representations for illustrating embodiments of this disclosure.

[0027] As used herein, a "niobium oxide-containing" film or a "metal-niobium oxide" film can refer to a film or layer comprising niobium atoms, oxygen atoms, and atoms of a metal other than niobium. This film or layer may have A x Nb y O 1-x-y The stoichiometric composition of the , wherein A can be an alkali metal, alkaline earth metal, transition metal, rare earth metal, lanthanide metal or post-transition metal.

[0028] As used herein, the term “substrate” can refer to any one or more underlying materials that can be used or on which devices, circuits or films can be formed.

[0029] As used herein, the term "atomic layer deposition" (ALD) can refer to a vapor deposition process in which deposition cycles, preferably multiple consecutive cycles, are performed in a processing chamber. Typically, during each deposition cycle, one or more first precursors can be chemisorbed onto the deposition surface (e.g., a substrate surface or a previously deposited lower layer surface, such as material from a previous ALD cycle), forming a monolayer or sub-monolayer that may not readily react with another first precursor (i.e., a self-limiting reaction). Subsequently, if desired, one or more second precursors can be introduced into the processing chamber to convert the chemisorbed first precursor into the desired material on the deposition surface. Typically, the second precursor can be capable of further reacting with the first precursor. Furthermore, a purging step can be utilized during each cycle to remove excess first or second precursor from the processing chamber and / or excess reactants and / or reaction byproducts after the conversion of the chemisorbed first precursor. In addition, as used herein, the term “atomic layer deposition” may also refer to processes specified by related terms, such as “chemical vapor deposition,” “atomic layer epitaxy” (ALE), molecular beam epitaxy (MBE), gas source MBE or organometallic MBE, and chemical beam epitaxy when performed with alternating pulses of a precursor composition, a reactive gas, and a purge gas (e.g., an inert carrier gas).

[0030] As used herein, the term “deposition process” can refer to the introduction of precursors (and / or reactants) into a reaction chamber to deposit a layer on a substrate.

[0031] As used herein, the term "pulse" can refer to, for example, a procedure of providing a reactive precursor or reactant to a reaction chamber between two purges, between a purge and another pulse, or between two pulses. It should be understood that pulses can be implemented temporally, spatially, or both. For example, in the case of temporal pulses, pulsed steps can be used, such as in a time sequence in which one or more first precursors are provided to the reaction chamber and another pulse is used to provide one or more second precursors to the reaction chamber. In this case, the substrate on which the layer is deposited does not necessarily move during the purge-purge sequence. In some examples, the two pulses can be separated by a purge step. In the case of spatial pulses, the pulsed step can take the form of moving the substrate through a purge curtain to the pulse location, where one or more first precursors or reactants are continuously supplied, and then moving the substrate again through the same purge curtain or another purge curtain, where one or more second precursors or reactants are continuously supplied.

[0032] As used herein, the term "purge" can refer to a procedure in which an inert or substantially inert gas is supplied to the reaction chamber between two pulses of precursors that may react with each other. For example, a purge (e.g., using a rare gas) can be provided between a first precursor pulse and a second reactant pulse to avoid or at least minimize gas-phase interactions between the first and second precursors. It should be understood that purging can be performed temporally, spatially, or both. For example, in the case of temporal purging, a purging step can be used, for instance, in a time sequence of supplying a first precursor to the reaction chamber, supplying a purge gas to the reaction chamber, and supplying a second precursor to the reaction chamber, wherein the substrate on which the deposited layer is deposited does not move. In the case of spatial purging, the purging step can take the form of moving the substrate from a first position to which one or more first precursors are continuously supplied through a purge gas curtain, and then to a second position to which one or more second precursors are continuously supplied.

[0033] "Cyclic deposition process" is an example of "deposition process". The term "cyclic deposition process" or "cyclic deposition process" can refer to the sequential introduction of precursors (and / or reactants) into a reaction chamber to deposit a layer on a substrate, and includes processing techniques such as atomic layer deposition (ALD), cyclic chemical vapor deposition (cyclic CVD), and hybrid cyclic deposition processes that include ALD and cyclic CVD components.

[0034] As used herein, the term "subcycle" can refer to a cyclic deposition process that includes two or more unit cycles repeated a predetermined number of times. Such a combination of two or more subcycles can be referred to as a complete deposition cycle.

[0035] As used herein, the terms “membrane” and “thin film” can refer to any continuous or discontinuous structure and material deposited by the methods disclosed herein. For example, “membrane” and “thin film” can include 2D materials, nanorods, nanotubes, or nanoparticles, or even partial or complete molecular layers, partial or complete atomic layers, or atomic and / or molecular clusters. “Membrane” and “thin film” can include materials or layers with pinholes, but still at least partially continuous.

[0036] As used herein, the term "comprising" indicates that certain features are included, but it does not exclude the presence of other features, provided that they do not render the claims or embodiments unfeasible.

[0037] Numerous example materials are given throughout the embodiments of this disclosure, and it should be noted that the chemical formulas given for each example material should not be construed as limiting, and the non-limiting example materials given should not be limited by the given exemplary stoichiometry.

[0038] This disclosure includes a method for depositing metal-niobium oxide films via a cyclic deposition process. The cyclic deposition process may include a complete deposition cycle comprising at least a first sub-cycle for depositing metal and oxygen atoms and a second sub-cycle for depositing niobium and / or oxygen atoms. The metal-niobium oxide film can be deposited by repeating the complete deposition cycle once or multiple times, such that one or more metal oxide films and one or more niobium oxide films are deposited on a substrate. The cyclic deposition process disclosed herein can deposit metal-niobium oxide films having a dielectric constant greater than 60 and low leakage current. Furthermore, the cyclic deposition process disclosed herein can deposit metal-niobium oxide films at reduced deposition temperatures (e.g., below 450°C) and exhibits excellent conformal properties on the substrate.

[0039] A cyclic deposition process for depositing oxide films may include two or more sub-cycles, each sub-cycle including an ALD-type process for depositing two or more films (e.g., a metal oxide film and a niobium oxide film). In some embodiments, a first sub-cycle may include an ALD-type process for depositing a metal oxide film, and a deposition cycle (e.g., a unit cycle) may include exposing a substrate to a vapor-phase metal precursor and a first oxygen precursor. In some embodiments, a second sub-cycle may include an ALD-type process for depositing a niobium oxide film, and a deposition cycle (e.g., a unit cycle) may include first exposing a substrate to a vapor-phase niobium precursor and a second oxygen precursor. In some embodiments, the first oxygen precursor may be the same as the second oxygen precursor, while in other embodiments, the first oxygen precursor and the second oxygen precursor may be different.

[0040] In some embodiments, precursors can be separated by purging with an inert gas (e.g., argon (Ar) or nitrogen (N2)) to prevent gas-phase reactions between precursors and to achieve self-saturating surface reactions. In some embodiments, the substrate can be moved to contact different precursors separately. Excess chemicals and reaction byproducts (if any) can be removed from the substrate surface, for example, by purging the reaction space or by moving the substrate, before the substrate contacts the next precursor. Undesirable gaseous molecules can be efficiently removed from the reaction space by means of an inert purge gas. A vacuum pump can be used to assist purging. Alternatively, a purging step may not be present between precursor pulses, and in some embodiments, precursor pulses may overlap.

[0041] Figure 1 A reactor system 100 is shown, which can be constructed and arranged to perform the methods described herein, for example... Figure 2 and Figure 3 The methods described herein, and / or forming structural or device portions as described herein, for example Figure 6A and 6B The structure is as follows. In the illustrated example, reactor system 100 includes a reaction chamber 102, a metal precursor container 104, a niobium precursor container 105, a first oxygen precursor container 106, a second oxygen precursor container 108, an exhaust device 110, and a controller 113 for forming a metal-niobium oxide dielectric layer in a MIM capacitor. In some embodiments, reactor system 100 may further include one or more dopant precursor containers (not shown).

[0042] The metal precursor container 104 may include a metal precursor that can be supplied to the reaction chamber 102. The metal precursor may include alkali metals, alkaline earth metals, transition metals, rare earth metals, lanthanides, or post-transition metals. In various embodiments, the metal precursor may include bismuth (Bi), tantalum (Ta), titanium (Ti), aluminum (Al), gallium (Ga), tin (Sn), lead (Pb), indium (In), gallium (Ga), thallium (Tl), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), silver (Ag), hafnium (Hf), tungsten (W), rhenium (Re), iridium (Ir), platinum (Pt), and / or gold (Au). The metal precursor container 104 may include a container and one or more metal precursors as described herein, alone or in mixture with one or more carrier gases (e.g., rare gases).

[0043] In various embodiments, reactor system 100 can be used to form a metal-niobium oxide film comprising bismuth niobium oxide. In such embodiments, metal precursor container 104 may include a bismuth precursor. The bismuth precursor may include cyclopentadienyl ligands, amide ligands, imino ligands, amidine ligands, halide ligands, alkyl ligands, alkoxide ligands, diketone ligands, and / or diazabutadiene ligands.

[0044] Examples of cyclopentadienyl ligands may include cyclopentadienyl (Cp), methylcyclopentadienyl (MeCp), ethylcyclopentadienyl (EtCp), isopropylcyclopentadienyl (iPrCp), tert-butylcyclopentadienyl (tBuCp), trimethylsilylcyclopentadienyl (TMSCp), pentamethylcyclopentadienyl (Cp*), 1,2,4-triisopropylcyclopentadienyl (iPr3Cp) and / or 1,2,4-tritert-butylcyclopentadienyl (tBu3Cp). Examples of amide-type ligands may include dimethylamide (NMe2), diethylamide (NEt2), ethylmethylamide (NEtMe), diisopropylamide (NiPr2), tert-butylamide (NHtBu) and / or bis(trimethylsilyl)amide (N(SiMe3)2). Examples of imide-type ligands may include ethylimide (NEt), isopropylimide (NiPr), isobutylimide (NiBu), tert-butylimide (NtBu), and / or tert-pentylimide (NtPn). Examples of amidine-type ligands may include N,N'-diethylacetamidine (Et2AMD), N,N'-diisopropylacetamidine (iPr2AMD), N,N'-diisopropylformamitamidine (iPr2FMD), N,N'-di-tert-butylacetamidine (tBu2AMD), and / or N,N'-di-tert-butylformamitamidine (tBu2FMD). Examples of halide ligands may include fluorine (F), chlorine (Cl), bromine (Br), and / or iodine (I). Examples of alkyl ligands may include methyl (Me), ethyl (Et), isopropyl (iPr), tert-butyl (tBu), isobutyl (iBu), neopentyl (Np), phenyl (Ph), 2-[(dimethylamino)methyl]phenyl (dmamPh) and / or trimethylsilylmethyl (CH3SiMe3). Examples of alkoxide ligands may include methanol (OMe), ethanol (OEt), isopropoxide (OiPr), tert-butanol (OtBu), 1-methoxy-2-methyl-2-propanol (mmp), 2-dimethylaminoethanol (dmae), 1-dimethylamino-2-propanol (dmap), 1-dimethylamino-2-methyl-2-propanol (dmamp), 1-ethylmethylamino-2-methyl-2-propanol (emamp), 1-diethylamino-2-methyl-2-propanol (deamp), 1-diethylamino-2-methyl-2-butanol (dmamb), 1-ethylmethylamino-2-methyl-2-butanol (emamb) and / or 1-diethylamino-2-methyl-2-butanol (deamb), 2,3-dimethylbutanol (dmb). Exemplary diketo ligands may include acetylacetonate (acac), 2,2,6,6-tetramethylheptane-3,5-diketoate (thd), and / or 1,1,1,5,5,5-hexafluoropentane-2,5-diketoate (hfac).Examples of diazabutadiene-type ligands may include 1,4-di-tert-butyl-1,4-diaza-1,3-butadiene (tBu2DAD), 1,4-diisopropyl-1,4-diaza-1,3-butadiene (iPr2DAD), 1,4-di-sec-butyl-1,4-diaza-1,3-butadiene (sBu2DAD), and / or 1,4-di-tert-pentyl-1,4-diaza-1,3-butadiene (tPn2DAD). In some embodiments, the bismuth precursor may be selected from the following: bismuth(III) chloride (BiCl3), Bi(OtBu)3, Bi(mmp)3, Bi(dmb)3, Bi(NMe2)3, Bi(NMeEt)3, Bi[N(SiMe3)2]3, Bi(thd)3, BiMe3, BiPh3, BiPh2Me, BiMe2(dmamPh), Bi(CH2SiMe3)3, Bi(OCMe2iPr)3) and / or Bi(CH3)3.

[0045] In various embodiments, reactor system 100 can be used to form a metal-niobium oxide film comprising titanium niobium oxide. In such embodiments, metal precursor container 104 may include a titanium precursor. The titanium precursor may include the cyclopentadienyl ligand, amide ligand, imino ligand, amidine ligand, halide ligand, alkyl ligand, alkoxide ligand, diketone ligand, and / or diazabutadiene ligand described above. In some embodiments, the titanium precursor may be selected from the following: TiF4, TiCl4, TiBr4, TiI4, Ti(NMe2)4, Ti(NEtMe)4, Ti(NEt2)4, Ti(OMe)4, Ti(OEt)4, Ti(OiPr)4, Ti(OtBu)4, Ti(MeCp)(OiPr)3, TiCp*(OMe)3, TiCp(NMe2)4, Ti(EtCp)(NMe2)4, Ta(OMe)5, Ti(OiPr)2(NMe2)2, Ti(OiPr)2(thd)2, Ti(OiPr)3(iPr2AMD), Ti(Np)4, Ti(N(CH3)2)4, Ta(NMe2)5, Ta(N(CH3)2), Ti(Np)4, TiCp2((iPrN)2C(NHiPr)), Ti(Cp)CHT, Ti(CpMe5)(OMe)3, Ti(NEt2)4, -tetra(diethylamino)titanium, Ti(NEtMe)3(guanNEtMe), Ti(NMe2)3(dmap), Ti(NMe2)3(CpN), Ti(OEt)4, Ti(OiPr)2(dmae)2, Ti(OiPr)2(NMe2)2, Ti(OiPr)2(thd)2, and / or Ti(OiPr)3(iPr2AMD).

[0046] In various embodiments, reactor system 100 can be used to form a metal-niobium oxide film comprising tantalum niobium oxide. In such embodiments, metal precursor container 104 may include a tantalum precursor. The tantalum precursor may include the cyclopentadienyl ligand, amide ligand, imino ligand, amidine ligand, halide ligand, alkyl ligand, alkoxide ligand, diketone ligand, and / or diazabutadiene ligand described above. In some embodiments, the tantalum precursor may be selected from the following: TaF5, TaCl5, TaBr5, TaI5, Ta(NMe2)5, Ta(NEt2)5, Ta(NEtMe)5, Ta(NtBu)(NMe2)3, Ta(NtBu)(NEt2)3, Ta(NtBu)(NEtMe)3, Ta(NiPr)(NEtMe)3, Ta(NtPn)(NMe2)3, Ta(OEt)5, TaNp3Cl2, Ta(NtBu)Cl3, Ta(NtPn)Cl3, Ta(NtBu)(iPr2AMD)2(NMe2), (CH3O)5Ta, (CH3CH2O)5Ta, Ta(OEt)4(dmae), and / or TaNp3Cl2.

[0047] Return to reference Figure 1 The niobium precursor container 105 may include a niobium precursor that can be supplied to the reaction chamber 102. The niobium precursor may include the cyclopentadienyl ligand, amide ligand, imino ligand, amidine ligand, halide ligand, alkyl ligand, alkoxide ligand, diketone ligand and / or diazabutadiene ligand described above. In some embodiments, the niobium precursor may be selected from the following: NbF5, NbCl5, NbBr5, NbI5, Nb(OMe)5, Nb(OEt)5, Nb(OiPr)5, Nb(OtBu)5, Nb(NMe2)5, Nb(NEtMe)5, Nb(NEt2)5, Nb(NtBu)(NMe2)2(Cp), Nb(NtBu)(NEtMe)2(Cp), Nb(NtBu)(NEt2)2(Cp), Nb(NtBu)(NMe2)3, Nb(NtBu)(NEtMe)3, Nb(NtBu)(NEt2)3, Nb(NiPr)(NMe2)3, Nb(NiPr)(NEtMe)3, Nb(NiPr)(NEt2)3, Nb(NtPn)(NMe2)3. Nb(NtPn)(NEtMe)3, and / or Nb(NtPn)(NEt2)3. The niobium precursor container 105 may include a container and one or more niobium precursors, either alone or mixed with one or more carrier gases (e.g., rare gases), as described herein.

[0048] The first oxygen precursor container 106 may include a first oxygen precursor that can be supplied to the reaction chamber 102. The second oxygen precursor container 108 may include a second oxygen precursor that can be supplied to the reaction chamber 102. The first and / or second oxygen precursors may include molecular oxygen (O2), ozone (O3), hydrogen peroxide (H2O2), water (H2O), formic acid (HCOOH), nitrous oxide (N2O), nitrogen oxides (NO2), dinitrogen pentoxide (N2O5), dinitrogen tetroxide (N2O4), pyridine N-oxide (C5H5NO), and / or oxygen plasma. The first oxygen precursor container 106 and / or the second oxygen precursor container 108 may include a container and one or more oxygen precursors, either alone or mixed with one or more carrier gases (e.g., rare gases), as described herein.

[0049] In some embodiments, reactor system 100 may include an optional second set of one or more reaction chambers 112, which may be configured and arranged to form one or more electrode layers of a MIM capacitor. One or more reaction chambers 112 may be operatively coupled to a first metal precursor container 124, an optional second metal precursor container 125, a reactant container 126, and an optional reactant container 128. Reaction chambers 102 and 112 may include ALD reaction chambers.

[0050] Although eight containers 104, 105, 106, 108, 124, 125, 126, and 128 are shown, reactor system 100 may include any suitable number of containers. Containers 104, 105, 106, 108, 124, 125, 126, and 128 may be connected via lines 114, 115, 116, 118, 134, 135, 136, and 138 to one or more reaction chambers 102, 112, each of which may include a flow controller, valve, heater, etc. Exhaust device 110 may include one or more vacuum pumps. The exhaust device may be connected via one or more lines to one or more of reaction chambers 102 and 112.

[0051] In some embodiments, reaction chamber 102 may be further configured to form a dielectric layer in a MIM capacitor, wherein the dielectric layer comprises a metal-niobium oxide layer. The metal-niobium oxide layer may be a ternary compound comprising niobium atoms, oxygen atoms, and atoms of another metal besides niobium. An example of such a niobium oxide-containing layer may include bismuth niobium oxide (Bi). x Nb y O 1-x-y ), titanium dioxide niobium (Ti x Nb y O 1-x-y ), tantalum niobium oxide (Ta x Nb y O 1-x-yHafnium niobium oxide (HfxNbyO1-xy), aluminum niobium oxide (Al) x Nb y O 1-x-y ), tin oxide niobium (Ti x Nb y O 1-x-y Layers such as )

[0052] The controller 113 may include electronic circuitry and software to selectively operate valves, manifolds, heaters, pumps, and other components included in the reactor system 100. Such circuitry and components can be operated to introduce precursors, reactants, and purge gases from corresponding containers 104, 105, 106, 108, 124, 125, 126, and 128. For example, the controller 113 may control the flow of a metal precursor from metal precursor container 104 to reaction chamber 102, the flow of a niobium precursor from niobium precursor container 105 to reaction chamber 102, the flow of a first oxygen precursor from first oxygen precursor container 106 to reaction chamber 102, and / or the flow of a second oxygen precursor from second oxygen precursor container 108 to reaction chamber 102.

[0053] Controller 113 can control the timing of precursor pulses (e.g., pulses for metal precursors, pulses for niobium precursors, pulses for first oxygen precursors, pulses for second oxygen precursors, etc.), the temperature of the substrate and / or reaction chamber, the pressure within the reaction chamber, and various other operations to provide proper operation of reactor system 100. Controller 113 may include control software to electrically or mechanically control valves to control the inflow and outflow of precursors, reactants, and purge gases from reaction chambers 102, 112. Controller 113 may include modules, such as software or hardware components, like FPGAs or ASICs, that perform certain tasks. Modules may advantageously be configured to reside on addressable storage media of the control system and configured to perform one or more processes as described herein.

[0054] Other configurations of reactor system 100 are possible, including different numbers and types of precursor and oxygen reactant sources, and optionally, a purge gas container. Furthermore, it should be understood that numerous arrangements of valves, conduits, precursor containers, and purge gas containers exist to achieve the objective of selectively feeding gases into reaction chambers 102, 112. Additionally, for the sake of simplicity and to illustrate the system schematically, many components have been omitted, and such components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0055] During operation of reactor system 100, substrates (e.g., semiconductor wafers (not shown)) are transferred from, for example, a substrate transport system to reaction chambers 102, 112. Once the substrates have been transferred to reaction chambers 102, 112, one or more precursors (e.g., precursors, reactants, carrier gases, and / or purge gases) from containers 104, 105, 106, 108, 124, 125, 126, 128 are introduced into reaction chambers 102, 112. In some embodiments of this disclosure, reactor system 100 may be a batch reactor. In some embodiments, reactor system 100 may be a vertical batch reactor. In other embodiments, reactor system 100 may include a small batch reactor configured to accommodate 10 or fewer substrates, 8 or fewer substrates, 6 or fewer substrates, 4 or fewer substrates, or 2 or fewer substrates.

[0056] In some embodiments of this disclosure, an oxide film, such as a metal-niobium oxide film comprising a metal component, a niobium component, and an oxygen component, can be deposited using a cyclic deposition process. See also... Figure 2 and Figure 3 To understand this cyclic deposition process, we need a non-limiting example.

[0057] Figure 2 A flowchart illustrating an example of a process 200 for forming a metal-niobium oxide film on a substrate is shown. In some embodiments, process 200 may be a thermal ALD process or a plasma-enhanced ALD process. Process 200 may begin at step 202, which may involve providing the substrate in a reaction chamber (e.g., reaction chamber 102). In some embodiments, process 200 may be performed at a deposition temperature below 450°C, for example, at a deposition temperature in the range of 200°C to 300°C.

[0058] Process 200 may include one or more complete deposition cycles 224, wherein each complete deposition cycle includes a metal-oxidant sub-cycle 204 and / or a niobium sub-cycle 212. In some embodiments, the metal-oxidant sub-cycle 204, the niobium sub-cycle 212, and / or the complete deposition cycle 224 may be repeated multiple times to form a metal-niobium oxide film having a desired composition and / or thickness. The ratio of the number of times the metal-oxidant sub-cycle 204 to the number of times the niobium sub-cycle 212 is performed may be varied to adjust the stoichiometric concentration of the metal and / or the stoichiometric concentration of niobium in the metal-niobium oxide film to achieve a film with desired electrical properties.

[0059] Metal-oxidant subcycle 204 may include steps 206, 208, and 210. In step 206, the substrate may contact or be exposed to a metal precursor. The metal precursor may include a metal precursor available from metal precursor container 104. In step 208, the substrate may contact or be exposed to a first oxygen precursor. The first oxygen precursor may include an oxygen precursor available from first oxygen precursor container 106. In some embodiments, metal-oxidant subcycle 204 may be repeated multiple times before proceeding to niobium subcycle 212. In some embodiments, metal-oxidant subcycle 204 or niobium subcycle 212 may be repeated multiple times before performing one or more other subcycles. For example, metal-oxidant subcycle 204 may be repeated multiple times before performing niobium subcycle 212. In step 210, it may be determined whether metal-oxidant subcycle 204 needs to be repeated. If metal-oxidant subcycle 204 needs to be repeated (step 210: yes), process 200 may proceed to step 206. Otherwise (step 210: no), process 200 can proceed to niobium cycle 212.

[0060] In some embodiments, the metal precursor pulse for exposing the substrate to the metal precursor and the first oxygen precursor pulse for exposing the substrate to the first oxygen precursor may partially overlap. In some embodiments, the metal precursor pulse may be immediately followed by the first oxygen precursor pulse. In some embodiments, the metal precursor pulse and the first oxygen precursor pulse may be separated by a purging step to remove excess metal precursor or excess first oxygen precursor from the reaction chamber. In some embodiments, the metal-oxidant subcycle 204 may be an ALD process. In some embodiments, no additional precursor may be provided to the reaction chamber between steps 206 and 208 or before the start of steps 206 and 208.

[0061] The niobium sub-cycle 212 for introducing niobium components into a metal-niobium oxide film may include steps 214 and 216. In step 214, the substrate may be contacted with or exposed to a niobium precursor. The niobium precursor may include a niobium precursor available from niobium precursor container 105. In step 216, the substrate may be contacted with or exposed to a first oxygen precursor or a second oxygen precursor from step 208. The first oxygen precursor may include a first oxygen precursor available from first oxygen precursor container 106. The second oxygen precursor may include a second oxygen precursor available from second oxygen precursor container 108. In some embodiments, the first oxygen precursor may be different from the second oxygen precursor. For example, the first oxygen precursor may include water, while the second oxygen precursor may include ozone.

[0062] In some embodiments, the niobium sub-cycle 212 may be repeated multiple times. In step 220, it can be determined whether the niobium sub-cycle 212 needs to be repeated. If the niobium sub-cycle 212 needs to be repeated (step 220: Yes), then process 200 can proceed to step 214. Otherwise (step 220: No), process 200 proceeds to decision gate 222.

[0063] In some embodiments, the pulses of the niobium precursor and the first or second oxygen precursor may partially overlap. In some embodiments, the pulse of the niobium precursor may be immediately followed by the pulse of the first or second oxygen precursor. In some embodiments, the pulses of the niobium precursor and the pulses of the first or second oxygen precursor may be separated by a purging step to remove excess niobium precursor or excess first or second oxygen precursor from the reaction chamber. In some embodiments, the niobium sub-cycle 212 may be an ALD process. In some embodiments, no additional precursor may be provided to the reaction chamber between steps 214 and 216 or before the start of steps 214 and 216.

[0064] In some examples, process 200 may include repeating the complete deposition cycle 224 one or more times. For example, after completing the niobium sub-cycle 212, process 200 may continue using decision gate 222, which determines whether process 200 should continue or exit. Decision gate 222 may be based on the thickness of the deposited metal-niobium oxide film; for example, if the film thickness is insufficient (step 222: Yes), the process may return to step 206 of the metal-oxidant sub-cycle 204. Before returning to step 206, in some examples, the reaction chamber may be purged with one or more purge gases (e.g., inert gases). In other examples, purging may be skipped. Purging the reaction chamber may remove any excess precursors from the processing chamber and / or any excess reactants, radicals, ions, and / or reaction byproducts from the reaction chamber. If decision gate 222 determines that the thickness of the metal-niobium oxide film is sufficient (step 222: No), process 200 may exit.

[0065] The pulse lengths of the metal precursor pulse (e.g., for metal-oxidant subcycle 204), the first oxygen precursor pulse (e.g., for metal-oxidant subcycle 204 or niobium subcycle 212), the niobium precursor pulse (e.g., for niobium subcycle 212), and / or the second oxygen precursor pulse (e.g., for niobium subcycle 212) can be from about 0.05 seconds to about 5.0 seconds, including from about 0.1 seconds to about 3 seconds and from about 0.2 seconds to about 1.0 seconds. In some embodiments, the pulse lengths of one or more precursors can be the same or different.

[0066] Figure 3A flowchart illustrating an example of another process 300 for forming a metal-niobium oxide film on a substrate is shown. In some embodiments, process 300 may be a thermal ALD process or a plasma-enhanced ALD process. Process 300 may begin at step 302, which may include providing the substrate in a reaction chamber (e.g., reaction chamber 102). In some embodiments, process 300 may be performed at a deposition temperature below 450°C, for example, at a deposition temperature in the range of 200°C to 300°C.

[0067] Process 300 may include one or more complete deposition cycles 322, wherein each complete deposition cycle includes a metal-oxidant sub-cycle 304 and / or a niobium sub-cycle 312. In some embodiments, the metal-oxidant sub-cycle 304, the niobium sub-cycle 312, and / or the complete deposition cycle 322 may be repeated multiple times to form a metal-niobium oxide film having a desired composition and / or thickness. The ratio of the number of times the metal-oxidant sub-cycle 204 to the number of times the niobium sub-cycle 212 is performed may be varied to adjust the stoichiometric concentration of the metal and / or the stoichiometric concentration of niobium metal in the metal-niobium oxide film to achieve a film with desired electrical properties.

[0068] Metal-oxidant subcycle 304 may include steps 306, 308, and 310. In step 306, the substrate may contact or be exposed to a metal precursor. The metal precursor may include a metal precursor available from metal precursor container 104. In step 308, the substrate may contact or be exposed to a first oxygen precursor. The first oxygen precursor may include an oxygen precursor available from first oxygen precursor container 106. In some embodiments, metal-oxidant subcycle 304 may be repeated multiple times before proceeding to niobium subcycle 312. In some embodiments, metal-oxidant subcycle 304 or niobium subcycle 312 may be repeated multiple times before performing another subcycle once or multiple times. For example, metal-oxidant subcycle 304 may be repeated multiple times before performing niobium subcycle 312. In step 310, it may be determined whether metal-oxidant subcycle 304 needs to be repeated. If metal-oxidant subcycle 304 needs to be repeated (step 310: yes), process 300 may proceed to step 306. Otherwise (step 310: no), process 300 proceeds to niobium subcycle 312.

[0069] In some embodiments, the metal precursor pulse for exposing the substrate to the metal precursor and the first oxygen precursor pulse for exposing the substrate to the first oxygen precursor may partially overlap. In some embodiments, the metal precursor pulse may be immediately followed by the first oxygen precursor pulse. In some embodiments, the metal precursor pulse and the first oxygen precursor pulse may be separated by a purging step to remove excess metal precursor or excess first oxygen precursor from the reaction chamber. In some embodiments, the metal-oxidant subcycle 304 may be an ALD process. In some embodiments, no additional precursor may be provided to the reaction chamber between steps 306 and 308 or before the start of steps 306 and 308.

[0070] Niobium sub-cycle 312 for introducing niobium components into a metal-niobium oxide film may include step 314. In step 314, the substrate may be brought into contact with or exposed to a niobium precursor. The niobium precursor may include a niobium precursor available from niobium precursor container 105.

[0071] In some embodiments, the niobium sub-cycle 312 may be repeated multiple times. In step 316, it can be determined whether the niobium sub-cycle 212 needs to be repeated. If the niobium sub-cycle 212 needs to be repeated (step 316: Yes), then process 300 can proceed to step 314. Otherwise (step 316: No), process 300 proceeds to decision gate 318.

[0072] In some embodiments, the pulses of the niobium precursor and the first or second oxygen precursor in process 300 may partially overlap. In some embodiments, the pulse of the niobium precursor in process 300 may be immediately followed by the pulse of the first or second oxygen precursor. In some embodiments, the pulses of the niobium precursor and the first or second oxygen precursor in process 300 may be separated by a purging step to remove excess niobium precursor or excess first or second oxygen precursor from the reaction chamber. In some embodiments, the niobium sub-cycle 312 may be an ALD process. In some embodiments, no additional precursor may be provided to the reaction chamber before starting step 314.

[0073] In some examples, process 300 may include repeating the complete deposition cycle 322 one or more times. For example, after completing the niobium sub-cycle 312, process 300 may continue via decision gate 318, which determines whether process 300 should continue or exit. Decision gate 318 may be determined based on the thickness of the deposited metal-niobium oxide film; for example, if the film thickness is insufficient (step 318: Yes), the process may return to step 306 of the metal-oxidant sub-cycle 304. Before returning to step 306, in some examples, the reaction chamber may be purged with one or more purge gases (e.g., inert gases). In other examples, purging may be skipped. If, at decision gate 318, it is determined that the thickness of the metal-niobium oxide film is sufficient (step 318: No), process 300 may proceed to step 320.

[0074] In step 320, either the first oxygen precursor or the second oxygen precursor from step 308 may be provided inside the reaction chamber. Oxygen atoms from the first or second oxygen precursor may fill pores and / or defects in the metal-niobium oxide film formed via one or more complete deposition cycles 322. The first oxygen precursor may include a first oxygen precursor available from the first oxygen precursor container 106. The second oxygen precursor may include a second oxygen precursor available from the second oxygen precursor container 108. In some embodiments, the first oxygen precursor may be different from the second oxygen precursor. For example, the first oxygen precursor may include water, while the second oxygen precursor may include ozone.

[0075] The pulse lengths of the metal precursor pulse (e.g., for metal-oxidant subcycle 304), the first oxygen precursor pulse (e.g., for metal-oxidant subcycle 304), and / or the niobium precursor pulse (e.g., for niobium subcycle 312) can be from about 0.05 seconds to about 5.0 seconds, including from about 0.1 seconds to about 3 seconds and from about 0.2 seconds to about 1.0 seconds. In some embodiments, the pulse lengths for one or more precursors can be the same or different. In some embodiments, the first oxygen precursor pulse or the second oxygen precursor pulse in step 320 can be longer than the precursor pulses of metal-oxidant subcycle 304 and niobium subcycle 312.

[0076] In some embodiments, a removal process may follow the precursor pulse used to deliver one or more precursors into the reaction chamber during the ALD process, for example, to remove excess precursors and / or reaction byproducts from near the substrate surface. The removal process may include purging reaction byproducts and / or excess reactants between precursor pulses, for example, by evacuating the reaction chamber to purge excess reactants and / or reaction byproducts. In some embodiments, the removal process includes a purging process. Gases such as nitrogen (N2), argon (Ar), and / or helium (He) may be used as purging gases to help remove excess reactants and / or reaction byproducts. In some embodiments, the purging pulse may have a pulse length of about 1 second to about 20 seconds.

[0077] The stoichiometric ratio of niobium to metal in a metal-niobium oxide film strongly influences its dielectric constant. Different stoichiometric ratios can lead to the formation of different crystalline phases, resulting in varying dielectric properties, band gaps, and leakage currents. The stoichiometric ratio can be controlled during the ALD process to fine-tune the properties of the metal-niobium oxide film. For example, Figure 4A Experimental dielectric constants of bismuth niobium oxide (BiNbO) films with three different stoichiometric ratios of bismuth and niobium in a capacitor comprising a titanium nitride electrode and a palladium electrode are shown. Furthermore, a ruthenium liner is sandwiched between the titanium nitride electrode and the bismuth niobium oxide film, and another ruthenium liner is sandwiched between the palladium electrode and the bismuth niobium oxide film. Figure 4B The leakage currents obtained for different stoichiometric ratios are shown. For example... Figure 4A As shown, the dielectric constant of bismuth-niobium oxide films can be fine-tuned by controlling the stoichiometric ratio of bismuth to niobium. For example, 63.34% niobium and 36.66% tantalum can result in a dielectric constant higher than 50. Figure 4B As shown, the leakage current of bismuth-niobium oxide also varies with the stoichiometric ratio of bismuth to niobium. For example, when a voltage of 1 volt / meter is applied, bismuth-niobium oxide with 63.34% niobium and 36.66% bismuth may cause a leakage current of 10. -9 / cm 2 The leakage current of an ampere.

[0078] Figure 5A flowchart of a method 500 for manufacturing or fabricating a MIM capacitor or capacitor stack including a metal-niobium oxide dielectric layer according to exemplary embodiments of the present disclosure is shown. The metal-niobium oxide dielectric layer may be located between and / or in direct contact with two metal electrodes. However, the metal electrodes of the MIM capacitor may contribute to high leakage current, and therefore, a metal liner may be sandwiched between the electrodes of the MIM capacitor and the dielectric layer. The noble metal liner may be formed using an ALD or another deposition process and is formed of a material selected due to its high work function, such as iridium (Ir), ruthenium (Ru), platinum (Pt), or other noble metals. The electrodes of the MIM capacitor may be formed of titanium nitride (TiN) or another metal useful in MIM capacitors, while the dielectric layer may include a metal-niobium oxide film (e.g., bismuth niobium oxide (Bi).) x Nb y O 1-x-y ), titanium dioxide niobium (Ti x Nb y O 1-x-y ), tantalum niobium oxide (Ta x Nb y O 1-x-y ), Hafnium oxide (Hf) x Nb y O 1-x-y ), alumina and niobium (Al x Nb y O 1-x-y ), tin oxide niobium (Ti x Nb y O 1-x-y (etc.). The metal liner can be provided with a thickness of less than or equal to 5 nm, for example, between about 0.5 nm and about 5 nm, which can be sufficient to cover the electrode layer.

[0079] Each layer in a MIM capacitor or capacitor stack can be formed using any common formation technique, such as ALD (or ALD-like processes or other cyclic deposition processes), PVD, or CVD, which can be used to deposit the thin film or material layer described herein. Therefore, method 500 may be intended to include methods for deposition. Figure 6A and 6B Any useful process for the MIM capacitor or capacitor stack layer or film shown. Initial step 502 may involve providing a substrate in the reaction chamber, which may have undergone several processing steps useful in the manufacture of a complete DRAM, BEOL or other electronic device, and may be in the form of a silicon wafer or other useful substrate material.

[0080] In step 504, a first electrode layer may be formed above or on the upper surface of the substrate from step 502. In some embodiments, the first electrode layer may be formed by depositing a metal (e.g., titanium nitride (TiN)) thin film through one of the deposition processes described above. The metal layer or element providing the first electrode layer may be formed of other metals, conductive metal oxides, conductive metal silicides, conductive metal nitrides, and combinations thereof. The purpose of the first electrode in a MIM capacitor or other device may be to serve as a primary conductor.

[0081] Step 506 of method 500 may be optional and may be skipped to form a MIM capacitor without an electrode liner. Step 506 may include forming a thin layer or film that serves as a first electrode liner for the first electrode formed in step 504. Step 506 may include depositing a layer or film of noble metal on the upper surface or exposed surface of the first electrode layer from step 504 using PVD, ALD, or another useful deposition technique. In some embodiments of method 500, step 506 of forming the first electrode liner (and / or step 510 of forming the second electrode liner) may be performed using a cyclic deposition process (e.g., ALD, ALD-like processes, etc.) comprising multiple cycles. The first electrode liner (and / or the second electrode liner) may include alloys, stacks, nanolaminated materials, or combinations thereof, including one or more noble metals such as rhenium, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold. The first electrode liner (and / or the second electrode liner) may have a thickness of less than or equal to 5 nm. Various noble metals may be deposited in step 504 to form the first electrode liner. In some embodiments, a noble metal with a work function greater than about 5 eV can be selected.

[0082] In step 508, a metal-niobium oxide dielectric layer may be formed on or above the exposed upper surface of the first electrode liner formed in step 506 or the first electrode layer formed in step 504. The metal-niobium oxide dielectric layer 604 can be formed using the methods described in this disclosure. Figure 2 and 3 The metal-niobium oxide dielectric layer 604 is formed using the deposition method described herein. It may include A... x Nb y O 1-x-y Where A can be an alkali metal, alkaline earth metal, transition metal, rare earth metal, lanthanide metal, actinide metal, or post-transition metal. Non-limiting examples of materials for the niobium oxide dielectric layer may include bismuth niobium oxide (Bi). x Nb y O 1-x-y ), titanium dioxide niobium (Ti x Nb y O 1-x-y ), tantalum niobium oxide (Ta x Nb y O 1-x-y), Hafnium oxide (Hf) x Nb y O 1-x-y ), alumina and niobium (Al x Nb y O 1-x-y ), tin oxide niobium (Ti x Nb y O 1-x-y Metal-niobium oxide dielectric layers can have thicknesses ranging from 1 to 50 nm.

[0083] Next, step 510 of method 500 includes forming a thin layer or film, which serves as a second electrode liner for the second electrode layer to be formed later in step 512. As discussed above, similar to step 506, step 510 may be optional and can be skipped to form a MIM capacitor without an electrode liner. Step 510 may include depositing a layer or film of noble metal on the upper surface or exposed surface of the dielectric layer from step 508 using PVD, ALD, or another useful deposition technique. Like the first electrode liner formed in step 506, the second electrode liner may have a thickness of less than or equal to 5 nm. The thickness of the second electrode liner formed in step 510 may be equal to or different from the thickness of the first electrode liner formed in step 506. Various noble metals may be deposited in step 510 to form the second electrode liner, and the same noble metal may be used for both the first and second electrode liners, or the noble metal materials may be different to suit a specific MIM capacitor design.

[0084] In step 512, a second electrode layer may be formed above or on the upper surface of the second electrode liner from step 510 or the metal-niobium oxide dielectric layer from step 508. In one embodiment, the second electrode layer may be formed by depositing a thin film of metal (e.g., titanium nitride (TiN)) using one of the deposition processes described above. Method 500 may include additional steps (not shown). For example, in the case of etching the electrode, the electrode conductive material (e.g., metal) may be etched as usual, i.e., using an etching chemical suitable for etching bulk electrodes, and the liner may serve as an etching stop layer. Then, as part of capacitor fabrication, short and varied etching cycles may be used to penetrate the liner.

[0085] Figure 6A Some embodiments according to this disclosure are shown (e.g., using...) Figure 5A simplified cross-sectional view of a portion of a MIM capacitor or capacitor stack 600A manufactured by steps 502, 504, 508, and 512 of method 500. As shown, a first electrode layer 602 may be formed over a substrate 612. The first electrode layer 602 may include a metal (or other conductive material) film or layer (e.g., the thickness of TiN or other conductive material that can be used to form capacitor electrodes) deposited on an upper surface 614 of the substrate 612, such that the underside or surface of the first electrode layer 602 may be adjacent to or in contact with the upper surface 614 of the substrate 612.

[0086] A metal-niobium oxide dielectric layer 604 may be provided or deposited on the upper side or surface of the first electrode layer 602, such that the lower side or surface of the metal-niobium oxide dielectric layer 604 is in contact with or adjacent to the first electrode layer 602. The metal-niobium oxide dielectric layer 604 may include bismuth niobium oxide (Bi). x Nb y O 1-x-y ), Titanium niobium oxide (TixNbyO1-xy), Tantalum niobium oxide (Ta x Nb y O 1-x-y ), Hafnium oxide (Hf) x Nb y O 1-x-y ), alumina and niobium (Al x Nb y O 1-x-y ), tin oxide niobium (Ti x Nb y O 1-x-y ), etc. The metal-niobium oxide dielectric layer 604 can be achieved through the present disclosure. Figure 2 and 3 The deposition method described in the text was used to form it.

[0087] The MIM capacitor or capacitor stack 600A may also include a second electrode layer 606, which may be formed of a thin film or layer of a conductive material (such as TiN or another useful conductive material or metal, as discussed above). The second electrode layer 606 may be formed of the same metal as the first electrode layer 602, or it may be formed of a different metal to suit a specific MIM capacitor design. Similarly, the thicknesses of the first electrode layer 602 and the second electrode layer 606 may be equal (or substantially equal) or different. The second electrode layer 606 may be deposited with its lower surface or side adjacent to or in contact with the upper surface or side of the metal-niobium oxide dielectric layer 604.

[0088] Figure 6B Some embodiments according to this disclosure are shown (e.g., using...) Figure 5A simplified cross-sectional view of a portion of a MIM capacitor or capacitor stack 600B manufactured by steps 502, 504, 506, 508, 510, and 512 of method 500. As shown, a first electrode layer 602 may be formed over a substrate 612, wherein the first electrode layer 602 may include a metal (or other conductive material) film or layer.

[0089] A noble metal layer can be deposited to form a first electrode liner 608 on the first electrode layer 602. The first electrode liner 608 can be formed of iridium (Ir), ruthenium (Ru), platinum (Pt), or other noble metals. The first electrode liner 608 can include a thickness of less than or equal to 5 nm, for example, in the range of 0.5 to 5 nm, and can be formed to provide a cap over the first electrode layer 602, wherein the lower surface of the first electrode liner 608 covers the upper side or surface of the first electrode layer 602.

[0090] The stack 600B may also include a metal-niobium oxide dielectric layer 604, which may be provided or deposited on the upper side or surface of the first electrode liner 602, such that the upper side or surface of the first electrode liner 608 may contact or abut the metal-niobium oxide dielectric layer 604. In other words, in the capacitor stack 600B, the first electrode liner 608 may be sandwiched between the first electrode layer 602 and the metal-niobium oxide dielectric layer 604. The metal-niobium oxide dielectric layer 604 may be disposed in accordance with the present disclosure. Figure 2 and 3 The deposition method described herein forms the niobium oxide dielectric layer 604. The niobium oxide dielectric layer 604 may include bismuth niobium oxide (Bi). x Nb y O 1-x-y ), titanium dioxide niobium (Ti x Nb y O 1-x-y ), tantalum niobium oxide (Ta x Nb y O 1-x-y ), Hafnium oxide (Hf) x Nb y O 1-x-y ), alumina and niobium (Al x Nb y O 1-x-y ), tin oxide niobium (Ti x Nb y O 1-x-y )wait.

[0091] A second electrode liner 610 may be formed on the metal-niobium oxide dielectric layer 604 to provide a cap or barrier layer for the second electrode layer 606. The second electrode liner 610 may be formed of iridium (Ir), ruthenium (Ru), platinum (Pt), or other noble metals. The second electrode liner 610 may have a thickness of less than or equal to 5 nm, for example, in the range of 0.5 to 5 nm, and may be formed such that the lower surface of the second electrode liner 610 covers the upper side or surface of the metal-niobium oxide dielectric layer 604. The second electrode liner 610 may be formed of the same noble metal as the first electrode liner 608, having a matching or nearly matching thickness. Alternatively, the second electrode liner 610 may be formed of a different noble metal than the first electrode liner 608, and / or the second electrode liner 610 and the first electrode liner 608 may have different thicknesses.

[0092] The MIM capacitor or capacitor stack 600B may also include a second electrode layer 606, which may be formed of a thin film or layer of a conductive material (such as TiN or another useful conductive material or metal, as discussed above). The second electrode layer 606 may be formed of the same metal as the first electrode layer 602, or it may be formed of a different metal to suit a particular MIM capacitor design. Similarly, the thicknesses of the first electrode layer 602 and the second electrode layer 606 may be equal (or substantially equal) or different. The second electrode layer 606 may be deposited with its lower surface or side adjacent to or contacting the upper surface or side of the second electrode liner 610, whereby the second electrode liner 610 covers the second electrode layer 606.

[0093] The benefits, other advantages, and solutions to problems have been described herein with reference to specific embodiments. However, these benefits, advantages, solutions to problems, and any elements that may lead to or make more significant any benefit, advantage, or solution should not be construed as key, essential, or necessary features or elements of this disclosure.

[0094] References to features, advantages, or similar language throughout this specification do not imply that all features and advantages achievable with this disclosure should be included in any single embodiment of the invention. Rather, language relating to features and advantages is to be understood as indicating that a particular feature, advantage, or characteristic described in connection with an embodiment is included in at least one embodiment of the subject matter disclosed herein. Therefore, the discussion of features and advantages throughout this specification, as well as similar language, may refer to, but do not necessarily refer to the same embodiment.

[0095] Furthermore, the features, advantages, and characteristics described in this disclosure may be combined in any suitable manner in one or more embodiments. Those skilled in the art will recognize that the subject matter of this application may be practiced without one or more specific features or advantages of a particular embodiment. In other instances, additional features and advantages that may not be present in all embodiments of this disclosure may be recognized in certain embodiments. Furthermore, in some instances, well-known structures, materials, or operations have not been shown or described in detail to avoid obscuring aspects of the subject matter of this disclosure. No claim element is intended to invoke 35 U.S.SC 112(f) unless the element is explicitly stated using the phrase “means for…”.

[0096] The scope of this disclosure is limited only by the appended claims, wherein, unless expressly stated, the singular form of an element does not mean "one and only one," but rather "one or more." It should be understood that, unless specifically stated, references to "a," "an," and / or "the" can include one or more, and references to singular items can also include plural items. Furthermore, the term "a plurality of" can be defined as "at least two." As used herein, when used with a list of items, the phrase "at least one" means that different combinations of one or more of the listed items may be used, and that only one item from the list may be required. The item can be a particular object, thing, or category. Furthermore, when phrases like "at least one of A, B, and C" are used in the claims, the phrase is intended to be interpreted as meaning that A may exist alone in one embodiment, B may exist alone in one embodiment, C may exist alone in one embodiment, or any combination of elements A, B, and C may exist in a single embodiment; for example, A and B, A and C, B and C, or A, B, and C. In some cases, "at least one of items A, B and C" can mean, for example, but not limited to, two of items A, one of items B and ten of items C; four of items B and seven of items C; or some other suitable combination.

[0097] All scopes and ratio limits disclosed herein can be combined. Unless otherwise stated, the terms “first,” “second,” etc., are used herein only as labels and are not intended to impose any order, position, or rank requirement on the items referred to by these terms. Furthermore, references to items such as “second” do not require or exclude the existence of items such as “first” or lower numbered, and / or items such as “third” or higher numbered.

[0098] Any references to attachment, fixation, connection, etc., may include permanent, removable, temporary, partial, complete, and / or any other possible attachment options. Furthermore, any reference to non-contact (or similar phrases) may also include reduced contact or minimal contact. Certain terms such as “upper,” “lower,” “upper part,” “lower part,” “horizontal,” “vertical,” “left,” “right,” etc., may be used in the above description. These terms are used where applicable to provide some clarity when dealing with relative relationships. However, these terms do not imply absolute relationships, positions, and / or orientations. For example, for an object, the “upper” surface can simply become the “lower” surface by flipping the object. Nevertheless, it remains the same object.

[0099] Furthermore, instances of one element being "connected" to another element in this specification can include direct and indirect connections. A direct connection can be defined as one element being connected to another element and having some contact with the other element. An indirect connection can be defined as a connection between two elements that are not in direct contact with each other, but have one or more additional elements between the connected elements. Additionally, as used herein, securing one element to another element can include direct and indirect securing. Furthermore, as used herein, "adjacent" does not necessarily mean contact. For example, one element may be adjacent to another element without contacting it.

[0100] While exemplary embodiments of this disclosure are set forth herein, it should be understood that this disclosure is not limited thereto. For example, although reactor systems are described in conjunction with various specific configurations, this disclosure is not necessarily limited to these examples. Various modifications, variations, and enhancements may be made to the systems and methods described herein without departing from the spirit and scope of this disclosure.

[0101] The subject matter of this disclosure includes all novel and non-obvious combinations and sub-combinations of various systems, components and configurations, as well as other features, functions, actions and / or properties disclosed herein, and any and all equivalents thereof.

Claims

1. A method for depositing a niobium oxide-containing film on a substrate in a reaction chamber, the method comprising multiple complete deposition cycles, each complete deposition cycle comprising: Perform a metal-oxidant sub-cycle, wherein the metal-oxidant sub-cycle includes contacting the substrate with a metal precursor and a first oxygen precursor; and Perform a niobium sub-cycle, wherein the niobium sub-cycle includes contacting the substrate with the niobium precursor.

2. The method according to claim 1, wherein, The niobium subcycle also includes contacting the substrate with the niobium precursor and the first oxygen precursor.

3. The method according to claim 2, wherein, The niobium sub-cycle also includes contacting the substrate with the niobium precursor and a second oxygen precursor that is different from the first oxygen precursor.

4. The method according to claim 1, further comprising: After completing the multiple full deposition cycles, the first oxygen precursor is supplied to the reaction chamber.

5. The method according to claim 4, further comprising: After the completion of the plurality of complete deposition cycles, a second oxygen precursor, which is different from the first oxygen precursor, is supplied to the reaction chamber.

6. The method according to claim 1, further comprising: After contacting the substrate with at least one of the metal precursor, the first oxygen precursor, and the niobium precursor, excess of the precursor and at least one of the reaction byproducts are removed from the reaction chamber.

7. The method according to claim 1, further comprising: The deposition temperature in the reaction chamber was maintained below 450°C.

8. The method according to claim 1, wherein, The metal precursors include alkali metals, alkaline earth metals, transition metals, rare earth metals, lanthanides, actinides, or post-transition metals.

9. The method according to claim 1, wherein, The niobium oxide-containing film includes bismuth niobium oxide; and The metal precursor includes a bismuth precursor, which includes at least a cyclopentadienyl ligand, an amide ligand, an imino ligand, an amidine ligand, a halide ligand, an alkyl ligand, an alkoxide ligand, a diketone ligand, or a diazabutadiene ligand.

10. The method according to claim 1, wherein, The niobium oxide-containing film includes niobium titanium oxide; and The metal precursor includes a titanium precursor, which includes at least a cyclopentadienyl ligand, an amide ligand, an imino ligand, an amidine ligand, a halide ligand, an alkyl ligand, an alkoxide ligand, a diketone ligand, or a diazabutadiene ligand.

11. The method according to claim 1, wherein, The niobium oxide-containing film includes niobium tantalum oxide; and The metal precursor includes a tantalum precursor, which includes at least a cyclopentadienyl ligand, an amide ligand, an imino ligand, an amidine ligand, a halide ligand, an alkyl ligand, an alkoxide ligand, a diketone ligand, or a diazabutadiene ligand.

12. The method according to claim 1, wherein, The first oxygen precursor includes one or more of molecular oxygen, ozone, hydrogen peroxide, water, formic acid, nitrous oxide, nitrogen oxides, or dinitrogen pentoxide.

13. The method according to claim 1, wherein, The niobium precursor includes at least a cyclopentadienyl ligand, an amide ligand, an imino ligand, an amidine ligand, a halide ligand, an alkyl ligand, an alkoxide ligand, a diketone ligand, or a diazabutadiene ligand.

14. The method according to claim 1, wherein, The niobium oxide-containing film includes BiNbO4.

15. The method according to claim 1, wherein, The niobium oxide-containing film has a dielectric constant between 30 and 250.

16. A reactor, comprising: Reaction chamber used to support the substrate; A metal source, which is connected to the reaction chamber and configured to provide a metal precursor; A niobium source, which is connected to the reaction chamber and configured to provide niobium precursors; A first oxygen source is connected to the reaction chamber and configured to provide a first oxygen precursor; as well as A control system configured to control the reactor to perform multiple complete deposition cycles to deposit a niobium oxide-containing film on a substrate, wherein each complete deposition cycle includes: A metal-oxidant subcycle, comprising supplying a metal precursor from a metal source and a first oxygen precursor from a first oxygen source to the reaction chamber; and The niobium cycle includes supplying niobium precursors from a niobium source to the reaction chamber.

17. The reactor according to claim 16, wherein, The niobium subcycle also includes supplying the reaction chamber with a niobium precursor from the niobium source and a first oxygen precursor from the first oxygen source.

18. The reactor of claim 16, further comprising: A second oxygen source, connected to the reaction chamber and configured to provide a second oxygen precursor different from the first oxygen precursor, is provided. The niobium sub-cycle further includes supplying the reaction chamber with niobium precursors from the niobium source and second oxygen precursors from the second oxygen source.

19. The reactor according to claim 16, wherein, The control system is also configured to control the reactor to supply a first oxygen precursor from the first oxygen source to the reaction chamber after the completion of the plurality of full deposition cycles.

20. The reactor of claim 16, further comprising: A second oxygen source, connected to the reaction chamber and configured to provide a second oxygen precursor different from the first oxygen precursor, is provided. The control system is further configured to control the reactor to supply a second oxygen precursor from a second oxygen source to the reaction chamber after the completion of the plurality of complete deposition cycles.

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