Selective deposition of metal oxides by pulsed chemical vapor deposition.

Abstract

To provide a method for selectively depositing a metal oxide on a substrate.SOLUTION: In a workpiece 200 including a laminate film 220 deposited on a substrate 202, a method produces alternating layers of first and second metal oxide layers by sequentially repeating the step of exposing a substrate which has a passivated surface 206 and a non-passivated surface 204 to a first metal alkoxide precursor to selectively deposit the first metal oxide layer 210 on or over the non-passivated surface, and the step of exposing the substrate to a second metal alkoxide precursor to selectively deposit the second metal oxide layer 212 on the first metal oxide layer. Each of the first and second metal alkoxide precursors contains different types of metals which are selected from titanium, zirconium, hafnium, aluminum, or lanthanum. Since the metals in the first and second metal oxide layers are different, the laminate film 220 is maintained in the amorphous or non-crystalline property.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE

[0001] Embodiments of the present disclosure relate generally to deposition processes, and more particularly to vapor phase deposition processes for metal oxides. [Background technology]

[0002]

[0002] Reliably producing sub-half-micron features is one of the key technological challenges for the next generation of very large scale integration (VLSI) and ultra-large scale integration (ULSI) semiconductor devices. However, pushing the limits of circuit technology and shrinking dimensions in VLSI and ULSI technologies has placed increasing demands on processing power. Forming reliable gate structures on substrates is critical to the success of VLSI and ULSI, and in the ongoing effort to increase circuit density and quality on individual substrates and dies.

[0003]

[0003] As the geometric size limitations of structures used to form semiconductor devices compete with technological limitations, it becomes increasingly difficult to meet the need for structures with small critical dimensions and high aspect ratios, and for structures with certain desired materials to be precisely formed. Conventional selective deposition processes often cannot be efficiently confined to a designated small area of ​​the substrate, resulting in the formation of unwanted materials in undesired locations on the substrate. Therefore, the deposition material is generally formed globally across the surface of the substrate without selectivity, or is deposited in undesired locations on the substrate, making selective deposition processes difficult to achieve and often resulting in cross-contamination of the substrate surface.

[0004]

[0004] Therefore, there is a need for improved methods for selectively depositing metal oxides. Summary of the Invention

[0005]

[0005] The embodiments described and discussed herein provide methods for depositing metal oxide materials, such as laminate films that include alternating layers of two or more metal oxides. The metal oxide materials are amorphous because alloying two or more metal oxides prevents crystallization throughout the material.

[0006] In one or more embodiments, a method for forming a metal oxide material includes positioning a substrate in a process chamber, the substrate having one or more passivated surfaces and one or more non-passivated surfaces, and exposing the substrate to a first metal alkoxide precursor to produce a first metal oxide layer on or above the non-passivated surfaces, while the passivated surfaces remain at least substantially free of the first metal oxide layer. The first metal alkoxide precursor is thermally decomposed to produce the first metal oxide layer. The method also includes exposing the substrate to a second metal alkoxide precursor to produce a second metal oxide layer on the first metal oxide layer, while the passivated surfaces remain at least substantially free of the second metal oxide layer. The second metal alkoxide precursor is thermally decomposed to produce the second metal oxide layer. The method further includes sequentially exposing the substrate to the first and second metal alkoxide precursors to produce a laminate film comprising alternating first and second metal oxide layers, each of the first and second metal alkoxide precursors having a different metal selected from titanium, zirconium, hafnium, aluminum, or lanthanum.

[0007] In another embodiment, a method for forming a metal oxide material includes positioning a substrate in a process chamber, the substrate having one or more passivated surfaces and one or more non-passivated surfaces, and exposing the substrate to a first metal alkoxide precursor to selectively deposit or otherwise form a laminate film on the non-passivated surfaces, while the passivated surfaces remain at least substantially free of the laminate film. The laminate film includes two or more pairs of alternating first and second metal oxide layers. The first metal alkoxide precursor is thermally decomposed during a first pulsed chemical vapor deposition process to produce the first metal oxide layer. Similarly, the second metal alkoxide precursor is thermally decomposed during a second pulsed chemical vapor deposition process to produce the second metal oxide layer.

[0008]

[0008] In some embodiments, a method for forming a metal oxide material includes positioning a substrate in a processing chamber, the substrate having one or more passivated surfaces and one or more non-passivated surfaces, and exposing the substrate to a first metal alkoxide precursor to produce a first metal oxide layer on or above the non-passivated surfaces while the passivated surfaces remain at least substantially free of the first metal oxide layer, wherein the first metal alkoxide precursor is thermally decomposed to produce the first metal oxide layer while the substrate is maintained at a first temperature of about 150°C to about 350°C. The method also includes exposing the substrate to a second metal alkoxide precursor to produce a second metal oxide layer on the first metal oxide layer while the passivated surface remains at least substantially free of the second metal oxide layer, wherein the second metal alkoxide precursor is thermally decomposed to produce the second metal oxide layer while the substrate is maintained at a second temperature of about 150° C. to about 350° C. Each of the first metal oxide layer and the second metal oxide layer has a different metal oxide selected from titanium oxide, zirconium oxide, hafnium oxide, aluminum oxide, dopants thereof, or lanthanum oxide. The method also includes sequentially repeating the exposing of the substrate to the first metal alkoxide precursor and the second metal alkoxide precursor to produce a laminate film comprising alternating first and second metal oxide layers, wherein the laminate film is amorphous and the laminate film comprises from about 10 pairs to about 100 pairs of the first and second metal oxide layers.

[0009]

[0009] So that the above-mentioned features of the present disclosure can be understood in detail, a more particular description of the present disclosure briefly summarized above can be had by reference to embodiments, some of which are illustrated in the accompanying drawings. However, since the present disclosure may admit of other equally effective embodiments, it should be noted that the accompanying drawings illustrate only typical embodiments of the present disclosure and therefore should not be considered as limiting the scope of the present disclosure. [Brief explanation of the drawings]

[0010] [Figure 1]

[0010] FIG. 1 is a flow diagram of a process for producing a laminate film including a metal oxide material on a substrate according to one or more embodiments described and discussed herein. [Figure 2]

[0011] 1 illustrates a cross-sectional view of a laminate film according to one or more embodiments described and discussed herein. DETAILED DESCRIPTION OF THE INVENTION

[0011]

[0012] For ease of understanding, where possible, the same reference numerals have been used to designate identical elements that are common to multiple figures. It is envisioned that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.

[0012]

[0013] It should be noted, however, that the present disclosure may admit of other equally effective embodiments, and therefore the accompanying drawings illustrate only typical embodiments of the present disclosure and should not be considered as limiting the scope of the present disclosure.

[0013]

[0014] In one or more embodiments, a method is provided for forming a metal oxide material, for example, for selectively depositing a laminate film of metal oxides. Two or more metal alkoxide precursors are used during a pulsed chemical vapor deposition (CVD) process to form a laminate film on a substrate. The laminate film includes alternating layers of two different metal oxides, such as a first metal oxide layer and a second metal oxide layer, having different types of metals. Each of the metal oxide layers can independently be or include titanium oxide, zirconium oxide, hafnium oxide, aluminum oxide, lanthanum oxide, dopants thereof, or any combination thereof. It is believed that alloying two or more different metal oxide layers prevents crystallization, thereby rendering the metal oxide material non-crystalline or amorphous.

[0014]

[0015] Figure 1 is a flow diagram of a process 100 that can be used to selectively deposit a laminate film including a metal oxide material on a substrate or other surface. Figure 2 shows a cross-sectional view of a workpiece 200 including a laminate film 220 deposited on a substrate 202. The laminate film 220 is one example of different types of laminate films that can be produced by the process 100. The laminate film 220 and similar structures and devices can be or include back-end structures or devices, front-end structures or devices, interconnect structures or devices, passivation structures or devices, fin structures or devices, gate structures or devices, contact structures or devices, or any suitable structure or device used in microelectronics, such as semiconductor devices, display devices, photovoltaic devices, batteries or energy storage devices, and other devices.

[0015]

[0016] Process 100 includes operations 110-190 as shown in FIG. 1 . In operation 110, one or more substrates may be placed or positioned in a processing chamber. The processing chamber may be or include a CVD chamber, a pulsed CVD chamber, a plasma-enhanced CVD (PE-CVD) chamber, an atomic layer deposition (ALD) chamber, a plasma-enhanced ALD (PE-ALD) chamber, a thermal annealing chamber, and other types of chambers. In one or more examples, process 100 is performed in a thermal CVD chamber or a thermal ALD chamber, such as a Trillium® chamber commercially available from Applied Materials, Inc.

[0016]

[0017] Substrate 202 includes one or more non-passivated materials or surfaces 204 and one or more passivated materials or surfaces 206. The metal oxide material of laminate film 220 is selectively deposited on one type of surface relative to another type of surface. More specifically, laminate film 220 is selectively deposited or formed on non-passivated surfaces 204, while passivated surfaces 206 remain completely or substantially free of the metal oxide material that forms laminate film 220.

[0017]

[0018] The non-passivated surface 204 can be a hydrogen-terminated (-H) and / or hydroxyl-terminated (-OH) surface of a silicon substrate or silicon-containing material, a silicon oxide substrate or silicon oxide-containing material, a metal (e.g., copper, tungsten, cobalt, aluminum, alloys thereof), or a contact material, or variations thereof. In one or more examples, the non-passivated surface 204 is a hydrogen-terminated silicon surface underlying a silicon substrate or silicon-containing material. In other examples, the non-passivated surface 204 is a hydroxyl-terminated silicon oxide surface underlying a silicon oxide substrate or silicon oxide-containing material.

[0018]

[0019] The passivated surface 206 may be an alkyl-terminated surface and may be terminated with one or more alkyl groups, such as a methyl group (-CH), an ethyl group (-CHCH), a propyl group (-CHCHCH), a butyl group (-CHCHCHCH), other alkyl groups, or any combination thereof. In one or more examples, the passivated surface 206 is a methyl-terminated surface, and the underlayer and / or substrate is or includes carbon-doped silicon oxide (SiCOH), such as Black Diamond® material commercially available from Applied Materials, Inc.

[0019]

[0020] In one or more embodiments, passivated surface 206 is or includes one or more dielectric materials, such as silicon oxide, doped silicon material, or low-k materials, such as carbon-containing materials. Suitable carbon-containing materials can be or include amorphous carbon, silicon carbide, carbon-doped silicon oxide materials, or combinations thereof. Exemplary low-k insulating dielectric materials can be or include silicon oxide materials, silicon nitride materials, carbon-doped silicon oxide materials, silicon carbide materials, carbon-based materials, or any combination thereof.

[0020]

[0021] In one or more examples, the non-passivated surface 204 is terminated with hydride groups, hydroxyl groups, or a combination thereof, and the passivated surface 206 is terminated with one or more alkyl groups.

[0021]

[0022] The substrate 202 is made of crystalline silicon (e.g., Si <100> or Si <111> The substrate 202 may be or include a material selected from silicon dioxide, strained silicon, silicon germanium, doped or undoped polysilicon, silicon-on-insulator (SOI) of doped or undoped silicon wafers and patterned or unpatterned wafers, carbon-doped silicon dioxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, or sapphire. The substrate 202 may have various dimensions (e.g., 200 mm, 300 mm, 450 mm, or other diameters) and may be a rectangular or square panel. Unless otherwise specified, the embodiments and examples described herein are performed on substrates with a diameter of 200 mm, 300 mm, or 450 mm. In embodiments in which an SOI structure is utilized for the substrate 202, the substrate 202 may include a buried dielectric layer disposed on a silicon crystalline substrate. In the embodiments shown herein, the substrate 202 may be a crystalline silicon substrate. Furthermore, the substrate 202 is not limited to any particular size or shape and can be a circular, polygonal, square, rectangular, curved, or non-circular workpiece, such as the polygonal glass substrates used in the manufacture of flat panel displays.

[0022]

[0023] In operation 120, workpiece 200 and / or substrate 202 are exposed to a first metal alkoxide precursor to produce a first metal oxide layer 210 on or above non-passivated surface 204, while passivated surface 206 is at least substantially, if not completely free, of first metal oxide layer 210. The metal of the first metal alkoxide precursor is selected from titanium, zirconium, hafnium, aluminum, or lanthanum, such that the deposited metal oxide included in first metal oxide layer 210 is selected from titanium oxide, zirconium oxide, hafnium oxide, aluminum oxide, lanthanum oxide, or dopants thereof.

[0023]

[0024] In operation 130, the workpiece 200 and / or substrate 202 including the first metal oxide layer 210 is exposed to a first purge gas. The first purge gas removes by-products, excess precursors, and other undesirable agents or contaminants. The first purge gas can be or can include nitrogen (N), argon, helium, or any combination thereof. The purge gas can have a flow rate of about 500 sccm to about 4,000 sccm, for example, about 500 sccm to about 1,000 sccm.

[0024]

[0025] In operations 120 and 130, a first metal alkoxide precursor is thermally decomposed during a first pulsed CVD process to produce a first metal oxide layer 210. The substrate 202 is heated and / or maintained at about 150° C. to about 450° C., e.g., about 200° C. to about 350° C., about 150° C. to about 350° C., or about 250° C. to about 300° C. during operations 120 and 130. The interior space or processing region of the CVD or other processing chamber may be maintained at a pressure of about 10 mTorr to about 10 Torr, e.g., about 100 mTorr to about 500 mTorr, during the first pulsed CVD process.

[0025]

[0026] The cycle of exposing the workpiece 200 and / or substrate 202 to the first metal alkoxide precursor and the first purge gas can be performed one or more times, for example, 2, 3, 5, about 10, about 15, about 20, about 25, about 30, about 40, about 50, about 65, about 80, about 100, or more times. The workpiece 200 and / or substrate 202 are sequentially exposed to the first metal alkoxide precursor and the first purge gas during the first pulsed CVD process.

[0026]

[0027] In one or more examples, the workpiece 200 and / or substrate 202 are exposed to the first metal alkoxide precursor for about 0.1 seconds to about 10 seconds, followed by exposure to the first purge gas for about 1 second to about 120 seconds. In other examples, the workpiece 200 and / or substrate 202 are exposed to the first metal alkoxide precursor for about 0.1 seconds to about 2 seconds, followed by exposure to the first purge gas for about 1 second to about 30 seconds.

[0027]

[0028] In operation 140, if the desired thickness of first metal oxide layer 210 is deposited or achieved, process 100 proceeds to operation 150. If the desired thickness of first metal oxide layer 210 is not deposited or achieved, operations 120 and 130 are repeated until the desired thickness of first metal oxide layer 210 is achieved. First metal oxide layer 210 can have a thickness of from about 0.05 nm to about 10 nm, e.g., from about 0.1 nm to about 5 nm, or from about 0.15 nm to about 1.2 nm.

[0028]

[0029] In operation 150, the workpiece 200 and / or substrate 202 are exposed to a second metal alkoxide precursor to produce a second metal oxide layer 212 on the first metal oxide layer 210, while the passivated surface 206 is at least substantially, if not completely, free of the second metal oxide layer 212. The metal of the second metal alkoxide precursor is selected from titanium, zirconium, hafnium, aluminum, or lanthanum such that the deposited metal oxide contained in the second metal oxide layer 212 has a metal that is different from the metal selected for the first metal oxide layer 210. Thus, the second metal oxide layer 212 comprises titanium oxide, zirconium oxide, hafnium oxide, aluminum oxide, lanthanum oxide, or dopants thereof. Thus, because the metal in the first metal oxide layer 210 is different from the metal in the second metal oxide layer 212, the laminate film 220 remains amorphous or non-crystalline.

[0029]

[0030] In operations 120 and 150, at least a first metal alkoxide precursor and / or a second metal alkoxide precursor are thermally decomposed by a β-hydride elimination process. The first metal alkoxide precursor and the second metal alkoxide precursor are thermally decomposed to produce a first metal oxide layer and a second metal oxide layer, respectively, in the absence of a co-reactant. In a typical CVD or ALD process, an oxidizing agent is used with a metal precursor to form a metal oxide. However, the deposition processes described and discussed herein rely on thermal decomposition, typically β-hydride elimination, to produce a metal oxide. The metal oxide precursor is both the metal source and the oxygen source. Therefore, the thermal decomposition of the metal alkoxide precursor is the sole source of both the metal and oxygen for the metal oxide layer. In one or more examples, there is no co-reactant, such as an oxidizing agent, that is independent of the metal alkoxide precursor in the pulsed CVD process. In other examples, one or more oxidizing agents (e.g., water, oxygen (O2), ozone, hydrogen peroxide, alcohols) may be used in conjunction with metal alkoxide precursors to produce metal oxide layers during a pulsed CVD process.

[0030]

[0031] In one or more embodiments, each of the first metal alkoxide precursor and the second metal alkoxide precursor independently is or includes one or more metal propoxide compounds (e.g., metal isopropoxide compounds) and / or one or more metal butoxide compounds (e.g., metal tert-butoxide compounds). As discussed above, the metal of the first metal alkoxide precursor is different from the metal of the second metal alkoxide precursor. In one or more examples, each of the first metal alkoxide precursor and the second metal alkoxide precursor is independently selected from the group consisting of titanium(IV) n-propoxide, titanium(IV) iso-propoxide, titanium(IV) n-butoxide, titanium(IV) tert-butoxide, hafnium(IV) n-propoxide, hafnium(IV) iso-propoxide, hafnium(IV) n-butoxide, hafnium(IV) tert-butoxide, zirconium(IV) n-propoxide, zirconium(IV) iso-propoxide The metal alkoxide precursor may be or include: zirconium(IV) n-butoxide, zirconium(IV) tert-butoxide, aluminum(III) n-propoxide, aluminum(III) iso-propoxide, aluminum(III) n-butoxide, aluminum(III) tert-butoxide, lanthanum(III) n-propoxide, lanthanum(III) iso-propoxide, lanthanum(III) n-butoxide, lanthanum(III) tert-butoxide, an isomer thereof, or any combination thereof. Other types of metal alkoxide precursors may be used in the processes described and discussed herein.

[0031]

[0032] In operation 160, the workpiece 200 and / or substrate 202 including the second metal oxide layer 212 are exposed to a second purge gas. The second purge gas removes by-products, excess precursors, and other undesirable agents or contaminants. The second purge gas can be or can include nitrogen (N), argon, helium, or any combination thereof. The purge gas can have a flow rate of about 500 sccm to about 4,000 sccm, for example, about 500 sccm to about 1,000 sccm.

[0032]

[0033] In operations 150 and 160, the second metal alkoxide precursor is thermally decomposed during a second pulsed CVD process to produce a second metal oxide layer 212. The substrate 202 is heated and / or maintained at about 150° C. to about 450° C., e.g., about 200° C. to about 350° C., about 150° C. to about 350° C., or about 250° C. to about 300° C. during operations 150 and 160. The interior space or processing region of the CVD or other processing chamber may be maintained at a pressure of about 10 mTorr to about 10 Torr, e.g., about 100 mTorr to about 500 mTorr, during the second pulsed CVD process.

[0033]

[0034] The cycle of exposing the workpiece 200 and / or substrate 202 to the second metal alkoxide precursor and the second purge gas can be performed one or more times, for example, 2, 3, 5, about 10, about 15, about 20, about 25, about 30, about 40, about 50, about 65, about 80, about 100, or more times. The workpiece 200 and / or substrate 202 are continuously exposed to the second metal alkoxide precursor and the second purge gas during the second pulsed CVD process.

[0034]

[0035] In one or more examples, the workpiece 200 and / or substrate 202 are exposed to the second metal alkoxide precursor for about 0.1 seconds to about 10 seconds, followed by exposure to the second purge gas for about 1 second to about 150 seconds. In other examples, the workpiece 200 and / or substrate 202 are exposed to the second metal alkoxide precursor for about 0.1 seconds to about 2 seconds, followed by exposure to the second purge gas for about 1 second to about 30 seconds.

[0035]

[0036] In operation 170, if the desired thickness of second metal oxide layer 212 is deposited or achieved, process 100 proceeds to operation 180. If the desired thickness of second metal oxide layer 212 is not deposited or achieved, operations 150 and 160 are repeated until the desired thickness of second metal oxide layer 212 is achieved. Second metal oxide layer 212 can have a thickness of about 0.05 nm to about 10 nm, e.g., about 0.1 nm to about 5 nm, or about 0.15 nm to about 1.2 nm.

[0036]

[0037] In operation 180, if the desired thickness of laminate film 220 is deposited, formed, or achieved, process 100 proceeds to operation 190, where process 100 is complete. If the desired thickness of laminate film 220 is not deposited, formed, or achieved, operations 120-170 are repeated until the desired thickness of laminate film 220 is achieved. For example, process 100 may include sequentially exposing workpiece 200 and / or substrate 202 to a first metal alkoxide precursor and a first purge gas in operations 120 and 130, and to a second metal alkoxide precursor and a second purge gas in operations 150 and 160, to produce laminate film 220 including alternating first and second metal oxide layers 210, 212. When operation 120 is repeated after operation 180 , first metal oxide layer 210 is deposited on second metal oxide layer 212 rather than on unpassivated surface 204 .

[0037]

[0038] Steps 120-170 are repeated until the laminate film 220 has a thickness of about 2 nm to about 100 nm, about 5 nm to about 50 nm, about 10 nm to about 35 nm, or about 15 nm to about 25 nm. Alternatively, operations 120-170 are repeated until a desired number of pairs of first and second metal oxide layers 210, 212 is achieved. The laminate film 220 includes about 2 pairs, about 5 pairs, about 10 pairs, about 20 pairs, about 30 pairs to about 40 pairs, about 50 pairs, about 80 pairs, about 100 pairs, about 150 pairs, about 200 pairs, or more pairs of first and second metal oxide layers 210, 212. In some examples, the laminate film 220 includes about 10 pairs to about 100 pairs of first and second metal oxide layers 210, 212. In other examples, the laminate film 220 includes from about 10 pairs to about 50 pairs, or from about 20 pairs to about 40 pairs of first and second metal oxide layers 210, 212.

[0038]

[0039] In one or more embodiments, the first metal oxide layer 210 comprises a first metal, and the second metal oxide layer 212 comprises a second metal different from the first metal. The laminate film 220 has an atomic ratio of the first metal to the second metal of about 5:1 to about 15:1, about 6:1 to about 12:1, or about 7:1 to about 10:1. In one or more examples of the laminate film 220, the first metal oxide layer 210 comprises titanium oxide, and the second metal oxide layer 212 comprises hafnium oxide. The atomic ratio of titanium to hafnium is about 5:1 to about 15:1, about 6:1 to about 12:1, or about 7:1 to about 10:1 in the laminate film 220.

[0039]

[0040] In one or more examples, the first metal oxide layer 210 comprising titanium oxide has a thickness of about 0.5 nm to about 2 nm, and the second metal oxide layer 212 comprising hafnium oxide has a thickness of about 0.08 nm to about 0.5 nm. In some examples, the first metal oxide layer 210 comprising titanium oxide has a thickness of about 0.8 nm to about 1.5 nm, and the second metal oxide layer 212 comprising hafnium oxide has a thickness of about 0.1 nm to about 0.3 nm. In other examples, the first metal oxide layer 210 comprising titanium oxide has a thickness of about 1 nm to about 1.2 nm, e.g., 1.14 nm, and the second metal oxide layer 212 comprising hafnium oxide has a thickness of about 0.12 nm to about 0.2 nm, e.g., 0.16 nm.

[0040]

[0041] Thus, a selective deposition process is provided for forming metal oxide materials on different surfaces, e.g., different portions, of a substrate by a selective CVD process, thereby obtaining structures with desired different types of materials formed at different locations on the substrate.

[0041]

[0042] Embodiments of the present disclosure further relate to one or more of clauses 1 to 33 below.

[0042]

[0043] 1. A method of forming a metal oxide material, comprising: positioning a substrate in a process chamber, the substrate including a passivated surface and an unpassivated surface; exposing the substrate to a first metal alkoxide precursor to produce a first metal oxide layer on or above the unpassivated surface, while the passivated surface remains at least substantially free of the first metal oxide layer, the first metal alkoxide precursor thermally decomposing to produce the first metal oxide layer; and exposing the substrate to a second metal alkoxide precursor to produce a second metal oxide layer on the first metal oxide layer, while the passivated surface remains at least substantially free of the second metal oxide layer. 1. A method of manufacturing a laminate film comprising: exposing a substrate to a second metal alkoxide precursor, wherein the second metal alkoxide precursor is thermally decomposed to produce a second metal oxide layer; and sequentially repeating the exposing of the substrate to the first and second metal alkoxide precursors to produce a laminate film comprising alternating first and second metal oxide layers, wherein the first and second metal alkoxide precursors independently comprise a metal selected from the group consisting of titanium, zirconium, hafnium, aluminum, and lanthanum, and the first and second metal alkoxide precursors have different metals.

[0043]

[0044] 2. A method for forming a metal oxide material, comprising: positioning a substrate in a processing chamber, the substrate comprising a passivated surface and an unpassivated surface; and selectively depositing a laminate film on the unpassivated surface while the passivated surface is at least substantially free of the laminate film, the laminate film comprising two or more pairs of alternating first and second metal oxide layers, a first metal alkoxide precursor being thermally decomposed during a first pulsed chemical vapor deposition process to produce the first metal oxide layer and a second metal alkoxide precursor being thermally decomposed during a second pulsed chemical vapor deposition process to produce the second metal oxide layer, the first metal alkoxide precursor and the second metal alkoxide precursor independently comprising a metal selected from the group consisting of titanium, zirconium, hafnium, aluminum, and lanthanum, and the first metal alkoxide precursor and the second metal alkoxide precursor having different metals.

[0044]

[0045] 3. A method of forming a metal oxide material, comprising: positioning a substrate in a process chamber, the substrate including a passivated surface and an unpassivated surface; exposing the substrate to a first metal alkoxide precursor to produce a first metal oxide layer on or above the unpassivated surface, while the passivated surface remains at least substantially free of the first metal oxide layer, the first metal alkoxide precursor being thermally decomposed to produce the first metal oxide layer, while the substrate is maintained at a first temperature of about 150°C to about 350°C; exposing the substrate to a second metal alkoxide precursor to produce a second metal oxide layer on the first metal oxide layer, while the passivated surface remains at least substantially free of the second metal oxide layer, the second metal alkoxide precursor being thermally decomposed to produce 1. A method of manufacturing a laminate film comprising: exposing a substrate to a second metal alkoxide precursor, wherein the second metal alkoxide precursor is maintained at a second temperature of about 150°C to about 350°C, to produce a second metal oxide layer; and sequentially repeating the exposing of the substrate to the first and second metal alkoxide precursors to produce a laminate film comprising alternating first and second metal oxide layers, wherein the laminate film comprises about 10 to about 100 pairs of first and second metal oxide layers, wherein the first and second metal oxide layers independently comprise a metal oxide selected from the group consisting of titanium oxide, zirconium oxide, hafnium oxide, aluminum oxide, lanthanum oxide, and dopants thereof, and the first and second metal oxide layers comprise different metal oxides.

[0045]

[0046] 4. The method of any one of clauses 1 to 3, wherein the substrate is maintained at a first temperature during the first pulsed chemical vapor deposition process and at a second temperature during the second pulsed chemical vapor deposition process, and each of the first temperature and the second temperature is independently from about 150°C to about 450°C.

[0046]

[0047] 5. The method of any one of clauses 1 to 4, wherein each of the first temperature and the second temperature is independently from about 200°C to about 350°C.

[0047]

[0048] 6. The method of any one of clauses 1 to 5, wherein each of the first metal oxide layer and the second metal oxide layer independently has a thickness of about 0.1 nm to about 5 nm, and the laminate film has about 10 pairs to about 50 pairs of the first metal oxide layer and the second metal oxide layer.

[0048]

[0049] 7. The method of any one of clauses 1 to 6, wherein the substrate is maintained at a temperature of about 150°C to about 450°C when forming the first metal oxide layer and / or the second metal oxide layer.

[0049]

[0050] 8. The method of any one of clauses 1 to 7, wherein the substrate is maintained at a temperature of about 200°C to about 350°C.

[0050]

[0051] 9. The method of any one of clauses 1 to 8, wherein the substrate is maintained at a temperature of about 250°C to about 300°C.

[0051]

[0052] 10. The method of any one of clauses 1 to 9, wherein the laminate film is amorphous.

[0052]

[0053] 11. The method of any one of clauses 1 to 10, wherein each of the first metal oxide layer and the second metal oxide layer independently has a thickness of from about 0.1 nm to about 5 nm.

[0053]

[0054] 12. The method of any one of clauses 1 to 11, wherein each of the first metal oxide layer and the second metal oxide layer independently has a thickness of from about 0.15 nm to about 1.2 nm.

[0054]

[0055] 13. The method of any one of clauses 1 to 12, wherein the laminate film comprises about 10 pairs to about 50 pairs of the first metal oxide layer and the second metal oxide layer.

[0055]

[0056] 14. The method of any one of clauses 1 to 13, wherein the laminate film comprises about 20 pairs to about 40 pairs of the first metal oxide layer and the second metal oxide layer.

[0056]

[0057] 15. The method of any one of clauses 1 to 14, wherein the laminate film has a thickness of about 5 nm to about 50 nm.

[0057]

[0058] 16. The method of any one of clauses 1 to 15, wherein the laminate film has a thickness of about 10 nm to about 35 nm.

[0058]

[0059] 17. The method of any one of clauses 1 to 16, wherein the laminate film has a thickness of about 15 nm to about 25 nm.

[0059]

[0060] 18. The method of any one of clauses 1 to 17, wherein the first metal oxide layer is produced during a first pulsed chemical vapor deposition process, and the substrate is sequentially exposed to a first metal alkoxide precursor and a first purge gas during the first pulsed chemical vapor deposition process, and the substrate is exposed to the first metal alkoxide precursor for about 0.1 seconds to about 10 seconds and to the first purge gas for about 1 second to about 120 seconds.

[0060]

[0061] 19. The method of any one of clauses 1 to 18, wherein the first metal oxide layer is produced during a first pulsed chemical vapor deposition process, and the substrate is sequentially exposed to a first metal alkoxide precursor and a first purge gas during the first pulsed chemical vapor deposition process, and the substrate is exposed to the first metal alkoxide precursor for about 0.1 seconds to about 2 seconds and to the first purge gas for about 1 second to about 30 seconds.

[0061]

[0062] 20. The method of any one of clauses 1 to 19, wherein the first purge gas can be or includes nitrogen (N2), argon, helium, or a combination thereof.

[0062]

[0063] 21. The method of any one of clauses 1 to 20, wherein the second metal oxide layer is produced during a second pulsed chemical vapor deposition process, and the substrate is sequentially exposed to a second metal alkoxide precursor and a second purge gas during the second pulsed chemical vapor deposition process, and the substrate is exposed to the second metal alkoxide precursor for about 0.1 seconds to about 10 seconds and to the second purge gas for about 1 second to about 120 seconds.

[0063]

[0064] 22. The method of any one of clauses 1 to 21, wherein the second metal oxide layer is produced during a second pulsed chemical vapor deposition process, and the substrate is sequentially exposed to a second metal alkoxide precursor and a second purge gas during the second pulsed chemical vapor deposition process, and the substrate is exposed to the second metal alkoxide precursor for about 0.1 seconds to about 2 seconds and to the second purge gas for about 1 second to about 30 seconds.

[0064]

[0065] 23. The method of any one of clauses 1 to 22, wherein the second purge gas can be or includes nitrogen (N2), argon, helium, or a combination thereof.

[0065]

[0066] 24. The method of any one of clauses 1 to 23, wherein the first metal alkoxide precursor and the second metal alkoxide precursor independently comprise a metal propoxide compound or a metal butoxide compound.

[0066]

[0067] 25. The method of any one of clauses 1 to 24, wherein the first metal alkoxide precursor and the second metal alkoxide precursor independently comprise a metal iso-propoxide compound or a metal tert-butoxide compound.

[0067]

[0068] 26. The first metal alkoxide precursor and the second metal alkoxide precursor are, independently, titanium(IV) n-propoxide, titanium(IV) iso-propoxide, titanium(IV) n-butoxide, titanium(IV) tert-butoxide, hafnium(IV) n-propoxide, hafnium(IV) iso-propoxide, hafnium(IV) n-butoxide, hafnium(IV) tert-butoxide, zirconium(IV) n-propoxide, zirconium(IV) iso-propoxide, zirconium(IV) n 26. The method of any one of clauses 1 to 25, comprising an aluminum(III) n-propoxide, aluminum(III) iso-propoxide, aluminum(III) n-butoxide, aluminum(III) tert-butoxide, lanthanum(III) n-propoxide, lanthanum(III) iso-propoxide, lanthanum(III) n-butoxide, lanthanum(III) tert-butoxide, an isomer thereof, or any combination thereof.

[0068]

[0069] 27. The method of any one of clauses 1 to 26, wherein the first metal oxide layer comprises titanium oxide and the second metal oxide layer comprises hafnium oxide.

[0069]

[0070] 28. The method of any one of clauses 1 to 27, wherein the first metal oxide layer comprises a first metal, the second metal oxide layer comprises a second metal, and the laminate film has an atomic ratio of the first metal to the second metal of about 5:1 to about 15:1.

[0070]

[0071] 29. The method of any one of clauses 1 to 28, wherein the first metal oxide layer comprises a first metal, the second metal oxide layer comprises a second metal, and the laminate film has an atomic ratio of the first metal to the second metal of about 6:1 to about 12:1.

[0071]

[0072] 30. The method of any one of clauses 1 to 29, wherein the first metal oxide layer comprises a first metal, the second metal oxide layer comprises a second metal, and the laminate film has an atomic ratio of the first metal to the second metal of about 7:1 to about 10:1.

[0072]

[0073] 31. The method of any one of clauses 1 to 30, wherein the non-passivated surface is terminated with hydride groups, hydroxyl groups, or a combination thereof, and the passivated surface is terminated with one or more alkyl groups.

[0073]

[0074] 32. The method of any one of clauses 1 to 31, wherein at least the first metal alkoxide precursor or the second metal alkoxide precursor is thermally decomposed by a β-hydride elimination process.

[0074]

[0075] 33. The method of any one of clauses 1 to 32, wherein at least a first metal alkoxide precursor or a second metal alkoxide precursor is thermally decomposed in the absence of a co-reactant to produce a first metal oxide layer or a second metal oxide layer.

[0075]

[0076] While the foregoing description is directed to embodiments of the present disclosure, other and further embodiments of the present disclosure may be devised without departing from the basic scope of the present disclosure, the scope of which is determined by the following claims. All documents set forth herein, including any priority documents and / or testing procedures, are incorporated herein by reference to the extent not inconsistent with this text. As is apparent from the foregoing summary and specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited to the forms of the present disclosure shown and described. Similarly, the term "comprising" is considered synonymous with the term "including" under U.S. law. Similarly, whenever a composition, element, or group of elements is preceded by the transitional phrase "comprising," it is understood that the same composition or group of elements having the transitional phrase "consisting essentially of," "consisting of," "selected from the group of consisting of," or "is" preceding such composition or list of one or more elements is also contemplated, and vice versa.

[0076]

[0077] Certain embodiments and features are described using a set of upper numerical limits and a set of lower numerical limits. It should be recognized that ranges including any two value combinations (e.g., any lower value with any upper value, any two lower values, and / or any two upper values) are contemplated unless otherwise specified. Specific lower limits, upper limits, and ranges are set forth in one or more claims below.

Claims

1. 1. A method of forming a metal oxide material, comprising: positioning a substrate in a processing chamber, the substrate comprising a passivated surface and a non-passivated surface, the non-passivated surface being terminated with hydride groups, hydroxyl groups, or a combination thereof; exposing the substrate to a first metal alkoxide precursor to produce the first metal oxide layer on or above the non-passivated surface while the passivated surface remains at least substantially free of a first metal oxide layer, the first metal alkoxide precursor being thermally decomposed to produce the first metal oxide layer; exposing the substrate to a second metal alkoxide precursor to produce the second metal oxide layer on the first metal oxide layer while the passivated surface remains at least substantially free of a second metal oxide layer, the second metal alkoxide precursor being thermally decomposed to produce the second metal oxide layer, the first metal alkoxide precursor and the second metal alkoxide precursor having different metals; sequentially repeating the exposure of the substrate to the first metal alkoxide precursor and the second metal alkoxide precursor to produce a laminate film comprising alternating layers of the first metal oxide layer and the second metal oxide layer; Including, The method, wherein the laminate film comprises 5 to 200 pairs of the first and second metal oxide layers.

2. The method of claim 1 , wherein the laminate film is amorphous.

3. The method of claim 1 , wherein the substrate is maintained at a temperature of 150° C. to 450° C. when forming the first metal oxide layer and / or the second metal oxide layer.

4. 10. The method of claim 1, wherein each of the first metal oxide layer and the second metal oxide layer independently has a thickness of 0.1 nm to 5 nm, and the laminate film has a thickness of 5 nm to 50 nm.

5. The method of claim 1 , wherein the laminate film comprises 10 to 50 pairs of the first metal oxide layer and the second metal oxide layer.

6. the first metal oxide layer is produced during a first pulsed chemical vapor deposition process; the substrate is sequentially exposed to the first metal alkoxide precursor and a first purge gas during the first pulsed chemical vapor deposition process; 10. The method of claim 1, wherein the substrate is exposed to the first metal alkoxide precursor for 0.1 to 10 seconds and to the first purge gas for 1 to 120 seconds.

7. the second metal oxide layer is produced during a second pulsed chemical vapor deposition process; the substrate is sequentially exposed to the second metal alkoxide precursor and a second purge gas during the second pulsed chemical vapor deposition process; 10. The method of claim 1, wherein the substrate is exposed to the second metal alkoxide precursor for 0.1 to 10 seconds and to the second purge gas for 1 to 120 seconds.

8. 10. The method of claim 1, wherein the first metal alkoxide precursor and the second metal alkoxide precursor independently comprise a metal selected from the group consisting of titanium, zirconium, hafnium, aluminum, and lanthanum.

9. The method of claim 1 , wherein the first metal alkoxide precursor and the second metal alkoxide precursor independently comprise a metal propoxide compound or a metal butoxide compound.

10. Each of the first metal alkoxide precursor and the second metal alkoxide precursor is independently selected from the group consisting of titanium(IV) n-propoxide, titanium(IV) iso-propoxide, titanium(IV) n-butoxide, titanium(IV) tert-butoxide, hafnium(IV) n-propoxide, hafnium(IV) iso-propoxide, hafnium(IV) n-butoxide, hafnium(IV) tert-butoxide, zirconium(IV) n-propoxide, zirconium(IV) iso-propoxide, zirconium(IV) 10. The method of claim 1, wherein the compound of formula (I) comprises ammonium(IV) n-butoxide, zirconium(IV) tert-butoxide, aluminum(III) n-propoxide, aluminum(III) iso-propoxide, aluminum(III) n-butoxide, aluminum(III) tert-butoxide, lanthanum(III) n-propoxide, lanthanum(III) iso-propoxide, lanthanum(III) n-butoxide, lanthanum(III) tert-butoxide, an isomer thereof, or any combination thereof.

11. The method of claim 1 , wherein the first metal oxide layer comprises titanium oxide and the second metal oxide layer comprises hafnium oxide.

12. 10. The method of claim 1, wherein the first metal oxide layer comprises a first metal, the second metal oxide layer comprises a second metal, and the laminate film has an atomic ratio of the first metal to the second metal of from 5:1 to 15:

1.

13. The method of claim 1 , wherein the passivated surface is terminated with one or more alkyl groups.

14. The method of claim 1 , wherein at least the first metal alkoxide precursor or the second metal alkoxide precursor is thermally decomposed by a β-hydride elimination process.

15. The method of claim 1 , wherein at least the first metal alkoxide precursor or the second metal alkoxide precursor is thermally decomposed in the absence of a co-reactant.

16. 1. A method of forming a metal oxide material, comprising: positioning a substrate in a processing chamber, the substrate comprising a passivated surface and a non-passivated surface, the non-passivated surface being terminated with hydride groups, hydroxyl groups, or a combination thereof; selectively depositing the laminate film onto the non-passivated surface while the passivated surface remains at least substantially free of the laminate film; Including, the laminate film includes two or more pairs of alternating first and second metal oxide layers; each of the first metal oxide layer and the second metal oxide layer independently has a thickness of 0.05 nm to 10 nm; a first metal alkoxide precursor is thermally decomposed during a first pulsed chemical vapor deposition process to produce said first metal oxide layer; a second metal alkoxide precursor is thermally decomposed during a second pulsed chemical vapor deposition process to produce said second metal oxide layer; the first metal alkoxide precursor and the second metal alkoxide precursor have different metals; the substrate is maintained at a first temperature during the first pulsed chemical vapor deposition process and at a second temperature during the second pulsed chemical vapor deposition process; The method, wherein each of the first temperature and the second temperature is independently from 150°C to 450°C.

17. 17. The method of claim 16, wherein the first metal alkoxide precursor and the second metal alkoxide precursor each independently comprise a metal selected from the group consisting of titanium, zirconium, hafnium, aluminum, and lanthanum.

18. 18. The method of claim 17, wherein each of the first temperature and the second temperature is independently from 200°C to 350°C.

19. each of the first metal oxide layer and the second metal oxide layer independently has a thickness of 0.1 nm to 5 nm; 17. The method of claim 16, wherein the laminate film has 10 to 50 pairs of the first metal oxide layer and the second metal oxide layer.

20. 1. A method of forming a metal oxide material, comprising: positioning a substrate in a processing chamber, the substrate comprising a passivated surface and a non-passivated surface, the non-passivated surface being terminated with hydride groups, hydroxyl groups, or a combination thereof; exposing the substrate to a first metal alkoxide precursor to produce the first metal oxide layer on or above the non-passivated surface while the passivated surface remains at least substantially free of a first metal oxide layer, wherein the first metal alkoxide precursor is thermally decomposed to produce the first metal oxide layer while the substrate is maintained at a first temperature of 150°C to 350°C; exposing the substrate to a second metal alkoxide precursor to produce the second metal oxide layer on the first metal oxide layer while the passivated surface remains at least substantially free of a second metal oxide layer, wherein the second metal alkoxide precursor is thermally decomposed to produce the second metal oxide layer while the substrate is maintained at a second temperature of 150°C to 350°C; sequentially repeating the exposing of the substrate to the first metal alkoxide precursor and the second metal alkoxide precursor to produce a laminate film comprising alternating layers of the first metal oxide layer and the second metal oxide layer, wherein the laminate film is amorphous and the laminate film comprises 10 to 100 pairs of the first metal oxide layer and the second metal oxide layer; Including, each of the first metal oxide layer and the second metal oxide layer independently has a thickness of 0.05 nm to 10 nm; the first metal oxide layer and the second metal oxide layer comprise different metal oxides; method.

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