Selective deposition of metal oxides using pulsed chemical vapor deposition

Abstract

Embodiments described and discussed herein provide a method for selectively depositing a metal oxide on a substrate. In one or more embodiments, a method for forming a metal oxide material includes positioning a substrate within a processing chamber, where the substrate has passivated and unpassivated surfaces, exposing the substrate to a first metal alkoxide precursor to selectively deposit a first metal oxide layer on or over the unpassivated surface, and removing the first metal oxide layer from the first metal alkoxide precursor. And exposing the substrate to a second metal alkoxide precursor to selectively deposit a second metal oxide layer on the first metal oxide layer. The method also includes sequentially repeating exposure of the substrate to the first and second metal alkoxide precursors to produce a laminated film containing alternating layers of the first and second metal oxide layers. The first and second metal alkoxide precursors each contain a different kind of metal selected from titanium, zirconium, hafnium, aluminum or lanthanum.

Description

[0001] This application is a divisional application of the patent application with the application date of February 2, 2021, the application number of 202180027095.4, and the invention title of "Selective Deposition of Metal Oxides by Pulsed Chemical Vapor Deposition". Technical Field

[0002] Embodiments of the present disclosure generally relate to deposition processes, and more particularly to gas phase deposition processes for metal oxides. Background Art

[0003] Reliably producing sub-half micron and smaller feature structures is one of the key technical challenges for the next generation of very large scale integrated circuits (VLSIs) and ultra-large scale integrated circuits (ULSIs) of semiconductor devices. However, as the limitations of circuit technology have advanced, the reduced feature sizes of VLSI and ULSI technologies have placed additional demands on processing capabilities. The reliable formation of gate structures on a substrate is important for the success of VLSI and ULSI and for the continued effort to increase the circuit density and quality of each substrate and die.

[0004] As the geometric limits of the structures used to form semiconductor devices are affected by technological limitations, the need for the precise formation of structures with small critical dimensions and high aspect ratios using desired materials and structures with certain desired materials has become increasingly difficult to meet. Conventional selective deposition processes often cannot be effectively limited to a specified small area of the substrate, resulting in unwanted materials being formed at undesired locations on the substrate. Thus, the deposited material is typically formed globally over the entire surface of the substrate without selectivity, or is deposited at undesired locations on the substrate, making it difficult to achieve a selective deposition process and often causing cross-contamination on the substrate surface.

[0005] Therefore, there is a need for an improved method for selectively depositing metal oxides. Summary of the Invention

[0006] Embodiments described and discussed herein provide methods for depositing metal oxide materials, such as laminate films that deposit alternating layers of two or more metal oxide layers. Since the alloying of two or more metal oxides prevents crystallization of the overall material, the metal oxide material is amorphous.

[0007] In one or more embodiments, a method of forming a metal oxide material includes positioning a substrate in a processing chamber, where the substrate has one or more passivated surfaces and one or more unpassivated surfaces; exposing the substrate to a first metal alkoxide precursor to produce a first metal oxide layer over or on the unpassivated 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 repeating exposing the substrate to the first metal alkoxide precursor and the second metal alkoxide precursor to produce a laminate film having alternating layers of the first and second metal oxide layers. The first metal alkoxide precursor and the second metal alkoxide precursor each have a different metal selected from titanium, zirconium, hafnium, aluminum, or lanthanum.

[0008] In other embodiments, a method of forming a metal oxide material includes positioning a substrate in a processing chamber, where the substrate has one or more passivated surfaces and one or more unpassivated surfaces; and selectively depositing or otherwise forming a laminate film on the unpassivated surfaces, while the passivated surfaces remain at least substantially free of the laminate film. The laminate film contains two or more pairs of alternating layers of a first metal oxide layer and a second metal oxide layer. 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.

[0009] In some embodiments, a method of forming a metal oxide material includes: positioning a substrate in a processing chamber, wherein the substrate has one or more passivated surfaces and one or more unpassivated surfaces; and exposing the substrate to a first metal alkoxide precursor to produce a first metal oxide layer over or on the unpassivated 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 when 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 surfaces remain 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 when the substrate is maintained at a second temperature of about 150°C to about 350°C. The first metal oxide layer and the second metal oxide layer each have a different metal oxide selected from titanium oxide, zirconium oxide, hafnium oxide, aluminum oxide, dopants of the foregoing, or lanthanum oxide. The method also includes: sequentially repeating the exposure of the substrate to the first metal alkoxide precursor and the second metal alkoxide precursor to produce a laminate film having alternating layers of the first and second metal oxide layers, wherein the laminate film is amorphous and wherein the laminate film contains from about 10 pairs to about 100 pairs of the first and second metal oxide layers. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] A more particular description of the present disclosure, briefly summarized above, may be obtained by reference to the embodiments, some of which are illustrated in the accompanying drawings. Accordingly, the above-described features of the present disclosure may be understood in detail, however, it should be noted that the drawings illustrate only typical embodiments of the present disclosure and are therefore not to be considered limiting of the scope of the present disclosure, as the present disclosure may admit other equivalent embodiments.

[0011] Figure 1 is a flow chart of a process for producing a laminate film containing a metal oxide material on a substrate in accordance with one or more embodiments described and discussed herein.

[0012] Figure 2 depicts a cross-sectional view of a laminate film in accordance with one or more embodiments described and discussed herein.

[0013] For ease of understanding, identical reference numerals have been used, where possible, to refer to the same elements common to the figures. It is contemplated that elements and features of one embodiment may be advantageously incorporated into other embodiments without further recitation.

[0014] However, it should be noted that the drawings illustrate only exemplary embodiments of the present disclosure and are therefore not to be considered limiting of the scope of the present disclosure, as the present disclosure may admit other equivalent embodiments. Detailed Implementation Manner

[0015] In one or more embodiments, a method for forming a metal oxide material is provided, such as selectively depositing a laminated film of metal oxide. Two or more metal alkoxide precursors are used during a pulsed chemical vapor deposition (CVD) process to form a laminated film on a substrate. The laminated film contains alternating layers of two different metal oxides having different kinds of metals, such as a first metal oxide layer and a second metal oxide layer. These metal oxide layers can each independently be or include titanium oxide, zirconium oxide, hafnium oxide, aluminum oxide, lanthanum oxide, dopants of the foregoing, or any combination of the foregoing. It is believed that alloying of two or more different metal oxide layers prevents crystallization, thus providing a metal oxide material that will be non-crystalline or amorphous.

[0016] Figure 1 is a flowchart of process 100, which can be used to selectively deposit a laminated film containing a metal oxide material on a substrate or other surface. Figure 2 A cross-sectional view of workpiece 200 depicting a laminated film 220 disposed on substrate 202 is shown. Laminated film 220 is an example of a laminated film of different kinds that can be produced by process 100. Laminated 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, gate structures or devices, contact structures, or any suitable structures or devices used in microelectronics, such as semiconductor devices, display devices, optoelectronic devices, batteries or energy storage devices, and other devices.

[0017] Process 100 includes operations 110-190, as Figure 1 shown. In operation 110, one or more substrates can be placed or otherwise positioned in a processing chamber. The processing chamber can 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 kinds of chambers. In one or more instances, process 100 is performed in a thermal pulsed CVD chamber or a thermal ALD chamber, such as a chamber commercially available from Applied Materials, Inc. chamber.

[0018] The substrate 202 includes one or more unpassivated materials or surfaces 204 and one or more passivated materials or surfaces 206. The metal oxide material of the stack film 220 is selectively deposited on one type of surface as compared to another type of surface. More specifically, the stack film 220 is selectively deposited or otherwise formed on the unpassivated surface 204, while the passivated surface 206 remains completely or substantially free of the metal oxide material of the stack film 220.

[0019] The unpassivated surface 204 can be a silicon substrate or silicon-containing material, a silicon oxide substrate or silicon oxide-containing material, a metal (e.g., copper, tungsten, cobalt, aluminum, an alloy of the foregoing), or a contact material, or a hydrogen-terminated (-H) surface and / or a hydroxyl-terminated (-OH) surface of various variations of the foregoing. In one or more instances, the unpassivated surface 204 is a hydrogen-terminated silicon surface, where the underlying layer is a silicon substrate or silicon-containing material. In other instances, the unpassivated surface 204 is a hydroxyl-terminated silicon oxide surface, where the underlying layer is a silicon oxide substrate or silicon oxide-containing material.

[0020] The passivated surface 206 can be an alkyl-terminated surface and can be terminated with one or more alkyl groups, such as methyl (-CH3), ethyl (-CH2CH3), propyl (-CH2CH2CH3), butyl (-CH2 CH2CH2CH3), other alkyl groups, or any combination of the foregoing. In one or more instances, the passivated surface 206 is a methyl-terminated surface, where the underlying layer and / or substrate is or includes a carbon-doped silicon oxide (SiCOH) material, e.g., Black material commercially available from Applied Materials.

[0021] In one or more embodiments, the passivated surface 206 is or includes one or more dielectric materials, such as silicon oxide, doped silicon material, or a low-k material, such as a carbon-containing material. Suitable carbon-containing materials can be or include amorphous carbon, silicon carbide, carbon-doped silicon oxide materials, or a combination of the foregoing. 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 of the foregoing.

[0022] In one or more instances, the unpassivated surface 204 is terminated with a hydride group, a hydroxide group, or a combination of the foregoing, while the passivated surface 206 is terminated with one or more alkyl groups.

[0023] The substrate 202 can be or include a material selected from the following: crystalline silicon (e.g., Si<100> or Si<111>), silicon oxide, strained silicon, silicon germanium, doped or undoped polysilicon, doped or undoped silicon wafers and patterned or unpatterned wafers, silicon-on-insulator (SOI), carbon-doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire. The substrate 202 can have various sizes, such as 200 mm, 300 mm, 450 mm or other diameters, and be a rectangular or square panel. Unless otherwise specified, the embodiments and examples described herein are carried out on substrates having substrates with 200 mm diameter, 300 mm diameter, or 450 mm diameter. In embodiments where an SOI structure is used for the substrate 202, the substrate 202 can include a buried dielectric layer disposed on a silicon crystalline substrate. In the embodiments described herein, the substrate 202 can be a crystalline silicon substrate. Additionally, the substrate 202 is not limited to any particular size or shape. The substrate 202 can be circular, polygonal, square, rectangular, curved or non-circular workpiece, such as a polygonal glass substrate used in the manufacture of flat panel displays.

[0024] In operation 120, the workpiece 200 and / or the substrate 202 are exposed to a first metal alkoxide precursor to produce a first metal oxide layer 210 over or on the unpassivated surface 204, while the passivated surface 206 remains at least substantially free (if not completely free) of the 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 contained in the first metal oxide layer 210 is selected from titanium oxide, zirconium oxide, hafnium oxide, aluminum oxide, lanthanum oxide, or dopants of the foregoing.

[0025] In operation 130, the workpiece 200 and / or the substrate 202 containing the first metal oxide layer 210 are exposed to a first purge gas. The first purge gas removes by-products, excess precursors, and other unwanted reagents or contaminants. The first purge gas can be or include nitrogen (N2), argon, helium, or any combination of the foregoing. The purge gas can have a flow rate of about 500 sccm to about 4,000 sccm, such as about 500 sccm to about 1,000 sccm.

[0026] During operations 120 and 130, the first metal alkoxide precursor is thermally decomposed during the first pulsed CVD process to produce the first metal oxide layer 210. The substrate 202 is heated and / or maintained at a temperature of about 150 °C to about 450 °C, such as 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 internal volume or processing zone of the CVD or other processing chamber can be maintained at a pressure of about 10 mTorr to about 10 Torr, such as about 100 mTorr to about 500 mTorr during the first pulsed CVD process.

[0027] The exposure of the workpiece 200 and / or the substrate 202 to the first metal alkoxide precursor and the first purge gas can be performed one or more times, such as 2 times, 3 times, 5 times, about 10 times, about 15 times, about 20 times, about 25 times, about 30 times, about 40 times, about 50 times, about 65 times, about 80 times, about 100 times, or more. The workpiece 200 and / or the substrate 202 are sequentially exposed to the first metal alkoxide precursor and the first purge gas during the first pulsed CVD process.

[0028] In one or more instances, the workpiece 200 and / or the substrate 202 are exposed to the first metal alkoxide precursor for a period of about 0.1 seconds to about 10 seconds, and then exposed to the first purge gas for a period of about 1 second to about 120 seconds. In other instances, the workpiece 200 and / or the substrate 202 are exposed to the first metal alkoxide precursor for a period of about 0.1 seconds to about 2 seconds, and then exposed to the first purge gas for a period of about 1 second to about 30 seconds.

[0029] During operation 140, if the deposition or otherwise reaches the desired thickness of the first metal oxide layer 210, the process 100 then proceeds to operation 150. If the deposition or otherwise has not reached the desired thickness of the first metal oxide layer 210, operations 120 and 130 are repeated until the desired thickness of the first metal oxide layer 210 is reached. The first metal oxide layer 210 can have a thickness of about 0.05 nm to about 10 nm, such as about 0.1 nm to about 5 nm or about 0.15 nm to about 1.2 nm.

[0030] In operation 150, the workpiece 200 and / or the 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 passivation surface 206 remains at least substantially free (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 different metal than the metal selected for the first metal oxide layer 210. Thus, the second metal oxide layer 212 contains titanium oxide, zirconium oxide, hafnium oxide, aluminum oxide, lanthanum oxide, or a dopant of the foregoing. Accordingly, since 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 uncrystallized.

[0031] In operations 120 and 150, at least the first metal alkoxide precursor and / or the 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 the first and second metal oxide layers, respectively, in the absence of a co-reactant. In a typical CVD or ALD process, an oxidant is used with the metal precursor to form a metal oxide. However, the deposition processes described and discussed herein rely on thermal decomposition and generally β-hydride elimination to produce the metal oxide. The metal oxide precursor is both a source of metal and a source of oxygen. Thus, the thermal decomposition of the metal alkoxide precursor is a single source for both the metal and the oxygen of the metal oxide layer. In one or more instances, there is no co-reactant such as an oxidant, and a co-reactant such as an oxidant is independent of the metal alkoxide precursor during a pulsed CVD process. In other instances, one or more oxidants (e.g., water, oxygen (O2), ozone, hydrogen peroxide, ethanol) may be used with the metal alkoxide precursor during a pulsed CVD process to produce the metal oxide layer.

[0032] In one or more embodiments, the first metal alkoxide precursor and the second metal alkoxide precursor are each independently or contain one or more metal propoxide compounds (e.g., metal iso-propoxide compounds) and / or one or more metal butoxide compounds (e.g., metal tert-butoxide compounds). As described above, the metal of the first metal alkoxide precursor is different from the metal of the second metal alkoxide precursor. In one or more instances, the first metal alkoxide precursor and the second metal alkoxide precursor are each independently or contain 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-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, isomers of the foregoing, or any combination of the foregoing. Other types of metal alkoxide precursors may be used in the processes described and discussed herein.

[0033] In operation 160, the workpiece 200 and / or the substrate 202 containing the second metal oxide layer 212 is exposed to a second purge gas. The second purge gas removes by-products, excess precursors, and other unwanted reagents or contaminants. The second purge gas may be or include nitrogen (N2), argon, helium, or any combination of the foregoing. The purge gas may have a flow rate of from about 500 sccm to about 4,000 sccm, such as from about 500 sccm to about 1,000 sccm.

[0034] In operations 150 and 160, the second metal alkoxide precursor is thermally decomposed during the second pulsed CVD process to produce the second metal oxide layer 212. The substrate 202 is heated and / or maintained at a temperature of from about 150 °C to about 450 °C, such as from about 200 °C to about 350 °C, from about 150 °C to about 350 °C, or from about 250 °C to about 300 °C, during operations 150 and 160. The internal volume or processing zone of the CVD or other processing chamber may be maintained at a pressure of from about 10 mTorr to about 10 Torr, such as from about 100 mTorr to about 500 mTorr, during the second pulsed CVD process.

[0035] The cycling of exposing the workpiece 200 and / or the substrate 202 to the second metal alkoxide precursor and the second purge gas can be performed one or more times, such as 2 times, 3 times, 5 times, about 10 times, about 15 times, about 20 times, about 25 times, about 30 times, about 40 times, about 50 times, about 65 times, about 80 times, about 100 times, or more. The workpiece 200 and / or the substrate 202 are sequentially exposed to the second metal alkoxide precursor and the second purge gas during the second pulsed CVD process.

[0036] In one or more instances, the workpiece 200 and / or the substrate 202 are exposed to the second metal alkoxide precursor for a period of about 0.1 second to about 10 seconds, and then exposed to the second purge gas for a period of about 1 second to about 150 seconds. In other instances, the workpiece 200 and / or the substrate 202 are exposed to the second metal alkoxide precursor for a period of about 0.1 second to about 2 seconds, and then exposed to the second purge gas for a period of about 1 second to about 30 seconds.

[0037] In operation 170, if the deposition or otherwise reaches the desired thickness of the second metal oxide layer 212, the process 100 then proceeds to operation 180. If the second metal oxide layer 212 has not been deposited or otherwise reached the desired thickness, operations 150 and 160 are repeated until the desired thickness of the second metal oxide layer 212 is reached. The second metal oxide layer 212 can have a thickness of about 0.05 nm to about 10 nm, such as about 0.1 nm to about 5 nm or about 0.15 nm to about 1.2 nm.

[0038] In operation 180, if the deposition, formation, or otherwise reaches the desired thickness of the stacked film 220, the process 100 then proceeds to operation 190, where the process 100 is completed. If the desired thickness of the stacked film 220 has not been deposited, formed, or otherwise reached, operations 120 - 170 are repeated until the desired thickness of the stacked film 220 is reached. For example, the process 100 includes sequentially repeating the exposure of the workpiece 200 and / or the substrate 202 to the first metal alkoxide precursor and the first purge gas in operations 120 and 130, and the exposure to the second metal alkoxide precursor and the second purge gas in operations 150 and 160 to produce a stacked film 220 containing alternating layers of the first and second metal oxide layers 210, 212. When operation 120 is repeated after operation 180, the first metal oxide layer 210 is deposited on the second metal oxide layer 212, rather than on the unpassivated surface 204.

[0039] Repeat operations 120 to 170 until the stacked 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, repeat operations 120 to 170 until the desired number of pairs of the first and second metal oxide layers 210, 212 is reached. The stacked film 220 contains about 2 pairs, about 5 pairs, about 10 pairs, about 20 pairs, or 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 the first and second metal oxide layers 210, 212. In some examples, the stacked film 220 contains about 10 pairs to about 100 pairs of the first and second metal oxide layers 210, 212. In other examples, the stacked film 220 contains about 10 pairs to about 50 pairs or about 20 pairs to about 40 pairs of the first and second metal oxide layers 210, 212.

[0040] In one or more embodiments, the first metal oxide layer 210 contains a first metal, and the second metal oxide layer 212 contains a second metal different from the first metal. The stacked 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 stacked film 220, the first metal oxide layer 210 contains titanium oxide, and the second metal oxide layer 212 contains hafnium oxide. The atomic ratio of titanium to hafnium for the stacked film 220 is about 5:1 to about 15:1, about 6:1 to about 12:1, or about 7:1 to about 10:1.

[0041] In one or more embodiments, the first metal oxide layer 210 containing titanium oxide has a thickness of about 0.5 nm to about 2 nm, and the second metal oxide layer 212 containing hafnium oxide has a thickness of about 0.08 nm to about 0.5 nm. In some embodiments, the first metal oxide layer 210 containing titanium oxide has a thickness of about 0.8 nm to about 1.5 nm, and the second metal oxide layer 212 containing hafnium oxide has a thickness of about 0.1 nm to about 0.3 nm. In other examples, the first metal oxide layer 210 containing titanium oxide has a thickness of about 1 nm to about 1.2 nm, such as 1.14 nm, and the second metal oxide layer 212 containing hafnium oxide has a thickness of about 0.12 nm to about 0.2 nm, such as 0.16 nm.

[0042] Accordingly, a selective deposition process is provided to form metal oxide materials on different surfaces (e.g., different portions) of a substrate by a selective CVD process. Thus, a structure having different desired types of materials formed at different positions on the substrate can be obtained.

[0043] Embodiments of the present disclosure further relate to any one or more of the following paragraphs 1-33:

[0044] 1. A method of forming a metal oxide material, comprising: positioning a substrate in a processing chamber, wherein the substrate includes a passivated surface and an unpassivated surface; exposing the substrate to a first metal alkoxide precursor to produce a first metal oxide layer over or on the unpassivated surface, while the passivated surface remains 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; 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; and sequentially repeating the exposure of the substrate to the first metal alkoxide precursor and the second metal alkoxide precursor to produce a laminated film comprising alternating layers of the first and second metal oxide layers, 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, and wherein the first metal alkoxide precursor and the second metal alkoxide precursor have different metals.

[0045] 2. A method of forming a metal oxide material, comprising: positioning a substrate in a processing chamber, wherein the substrate includes a passivated surface and an unpassivated surface; and selectively depositing a laminated film on the unpassivated surface, while the passivated surface remains at least substantially free of the laminated film, wherein: the laminated film comprises two or more pairs of alternating layers of a first metal oxide layer and a second metal oxide layer, the first metal alkoxide precursor is thermally decomposed during a first pulsed chemical vapor deposition process to produce the first metal oxide layer, the second metal alkoxide precursor is 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 comprise 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 have different metals.

[0046] 3. A method of forming a metal oxide material, comprising: positioning a substrate in a processing chamber, wherein the substrate includes a passivated surface and an unpassivated surface; exposing the substrate to a first metal alkoxide precursor to produce a first metal oxide layer over or on the unpassivated surface, while the passivated surface remains 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 when 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, wherein the second metal alkoxide precursor is thermally decomposed to produce the second metal oxide layer when the substrate is maintained at a second temperature of about 150°C to about 350°C; and sequentially repeating the exposure of the substrate to the first metal alkoxide precursor and the second metal alkoxide precursor to produce a laminated film including alternating layers of the first and second metal oxide layers, wherein the laminated film is amorphous, and wherein the laminated film includes about 10 pairs to about 100 pairs of the first and second metal oxide layers, wherein the first metal oxide layer and the second metal oxide layer independently include a metal oxide selected from the group consisting of titanium oxide, zirconium oxide, hafnium oxide, aluminum oxide, lanthanum oxide, and dopants of the foregoing, and wherein the first metal oxide layer and the second metal oxide layer contain different metal oxides.

[0047] 4. The method according to any one of paragraphs 1 to 3, wherein the substrate is maintained at the first temperature during a first pulsed chemical vapor deposition process and at the second temperature during a second pulsed chemical vapor deposition process, and wherein the first temperature and the second temperature are each independently in the range of about 150°C to about 450°C.

[0048] 5. The method according to any one of paragraphs 1 to 4, wherein the first temperature and the second temperature are each independently in the range of about 200°C to about 350°C.

[0049] 6. The method according to any one of paragraphs 1 to 5, wherein the first metal oxide layer and the second metal oxide layer each independently have a thickness of about 0.1 nm to about 5 nm, and wherein the laminated film includes about 10 pairs to about 50 pairs of the first and second metal oxide layers.

[0050] 7. The method according to any one of paragraphs 1 to 6, wherein when the first metal oxide layer and / or the second metal oxide layer is produced, the substrate is maintained at a temperature of about 150°C to about 450°C.

[0051] 8. The method according to any one of paragraphs 1 to 7, wherein the substrate is maintained at a temperature of about 200°C to about 350°C.

[0052] 9. The method according to any one of paragraphs 1 to 8, wherein the substrate is maintained at a temperature of about 250°C to about 300°C.

[0053] 10. According to the method of any one of paragraphs 1-9, wherein the laminated film is amorphous.

[0054] 11. According to the method of any one of paragraphs 1-10, wherein the first metal oxide layer and the second metal oxide layer each independently have a thickness of about 0.1 nm to about 5 nm.

[0055] 12. According to the method of any one of paragraphs 1-11, wherein the first metal oxide layer and the second metal oxide layer each independently have a thickness of about 0.15 nm to about 1.2 nm.

[0056] 13. According to the method of any one of paragraphs 1-12, wherein the laminated film comprises about 10 pairs to about 50 pairs of the first and second metal oxide layers.

[0057] 14. According to the method of any one of paragraphs 1-13, wherein the laminated film comprises about 20 pairs to about 40 pairs.

[0058] 15. According to the method of any one of paragraphs 1-14, wherein the laminated film has a thickness of about 5 nm to about 50 nm.

[0059] 16. According to the method of any one of paragraphs 1-15, wherein the laminated film has a thickness of about 10 nm to about 35 nm.

[0060] 17. According to the method of any one of paragraphs 1-16, wherein the laminated film has a thickness of about 15 nm to about 25 nm.

[0061] 18. According to the method of any one of paragraphs 1-17, wherein the first metal oxide layer is formed during a first pulsed chemical vapor deposition process, wherein 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 wherein the substrate is exposed to the first metal alkoxide precursor for a period of about 0.1 seconds to about 10 seconds and to the first purge gas for a period of about 1 second to about 120 seconds.

[0062] 19. According to the method of any one of paragraphs 1-18, wherein the first metal oxide layer is formed during a first pulsed chemical vapor deposition process, wherein 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 wherein the substrate is exposed to the first metal alkoxide precursor for a period of about 0.1 seconds to about 2 seconds and to the first purge gas for a period of about 1 second to about 30 seconds.

[0063] 20. According to the method of any one of paragraphs 1-19, wherein the first purge gas can be or include nitrogen (N2), argon, helium, or a combination of the foregoing.

[0064] 21. A method according to any one of paragraphs 1-20, wherein a second metal oxide layer is produced during a second pulsed chemical vapor deposition process, wherein 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 wherein the substrate is exposed to the second metal alkoxide precursor for a period of about 0.1 second to about 10 seconds and to the second purge gas for a period of about 1 second to about 120 seconds.

[0065] 22. A method according to any one of paragraphs 1-21, wherein a second metal oxide layer is produced during a second pulsed chemical vapor deposition process, wherein 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 wherein the substrate is exposed to the second metal alkoxide precursor for a period of about 0.1 second to about 2 seconds and to the second purge gas for a period of about 1 second to about 30 seconds.

[0066] 23. A method according to any one of paragraphs 1-22, wherein the second purge gas can be or include nitrogen (N2), argon, helium, or a combination of the foregoing.

[0067] 24. A method according to any one of paragraphs 1-23, wherein the first metal alkoxide precursor and the second metal alkoxide precursor independently include a metal propoxide compound or a metal butoxide compound.

[0068] 25. A method according to any one of paragraphs 1-24, wherein the first metal alkoxide precursor and the second metal alkoxide precursor independently include a metal isopropoxide compound or a metal tert-butoxide compound.

[0069] 26. A method according to any one of paragraphs 1-25, wherein the first metal alkoxide precursor and the second metal alkoxide precursor independently include titanium(IV) n-propoxide, titanium(IV) isopropoxide, titanium(IV) n-butoxide, titanium(IV) tert-butoxide, hafnium(IV) n-propoxide, hafnium(IV) isopropoxide, hafnium(IV) n-butoxide, hafnium(IV) tert-butoxide, zirconium(IV) n-propoxide, zirconium(IV) isopropoxide, zirconium(IV) n-butoxide, zirconium(IV) tert-butoxide, aluminum(III) n-propoxide, aluminum(III) isopropoxide, aluminum(III) n-butoxide, aluminum(III) tert-butoxide, lanthanum(III) n-propoxide, lanthanum(III) isopropoxide, lanthanum(III) n-butoxide, lanthanum(III) tert-butoxide, isomers of the foregoing, or any combination of the foregoing.

[0070] 27. A method according to any one of paragraphs 1-26, wherein the first metal oxide layer comprises titanium oxide and the second metal oxide layer comprises hafnium oxide.

[0071] 28. A method according to any one of paragraphs 1 to 27, wherein the first metal oxide layer comprises a first metal, the second metal oxide layer comprises a second metal, and wherein the laminate film has an atomic ratio of the first metal to the second metal of from about 5:1 to about 15:1.

[0072] 29. A method according to any one of paragraphs 1 to 28, wherein the first metal oxide layer comprises a first metal, the second metal oxide layer comprises a second metal, and wherein the laminate film has an atomic ratio of the first metal to the second metal of from about 6:1 to about 12:1.

[0073] 30. A method according to any one of paragraphs 1 to 29, wherein the first metal oxide layer comprises a first metal, the second metal oxide layer comprises a second metal, and wherein the laminate film has an atomic ratio of the first metal to the second metal of from about 7:1 to about 10:1.

[0074] 31. A method according to any one of paragraphs 1 to 30, wherein the unpassivated surface is capped with a hydride group, a hydroxide group, or a combination of the foregoing, and wherein the passivated surface is capped with one or more alkyl groups.

[0075] 32. A method according to any one of paragraphs 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.

[0076] 33. A method according to any one of paragraphs 1 to 32, wherein at least the first metal alkoxide precursor or the second metal alkoxide precursor is thermally decomposed to produce the first or second metal oxide layer in the absence of a co - reactant.

[0077] Although the foregoing is directed to embodiments of the present disclosure, other and further embodiments can be conceived without departing from the basic scope of the present disclosure, and the scope of the present disclosure is determined by the appended claims. All documents described herein are incorporated herein by reference, including any priority documents and / or experimental procedures not inconsistent with the content herein. As will be apparent from the foregoing general description as well as the specific embodiments, various modifications can be made without departing from the spirit and scope of the present disclosure when the forms of the present disclosure have been illustrated and described. Accordingly, it is not intended to limit the present disclosure thereto. Similarly, the term "comprising" is used herein as a synonym for the term "including". Similarly, whenever an element, component, or group of elements is recited with the transitional phrase "comprising" leading, it is understood that the same element, component, or group of elements with the transitional phrases "consisting essentially of", "consisting of", "selected from the group consisting of", or "is (are)" leading the recited element, component, or group of elements is also contemplated, and vice versa.

[0078] Certain embodiments and features have been described using a set of upper numerical limits and a set of lower numerical limits. Unless otherwise indicated, it should be understood that ranges including combinations of any two values are contemplated, e.g., combinations of any lower value with any upper value, combinations of any two lower values, and / or combinations of any two upper values. Certain lower limits, upper limits, and ranges appear in one or more of the claims that follow.

Claims

1. A method of forming a metal oxide material, comprising: Positioning a substrate in a processing chamber, wherein the substrate includes a passivated surface and an unpassivated surface, and wherein the unpassivated surface is capped with hydride groups, hydroxide groups, or a combination of the foregoing; Exposing the substrate to a first metal alkoxide precursor to produce a first metal oxide layer over or on the unpassivated surface, while the passivated surface remains 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; 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, and wherein the first metal alkoxide precursor and the second metal alkoxide precursor have different metals; and Sequentially repeating exposing the substrate to the first metal alkoxide precursor and the second metal alkoxide precursor to produce a laminated film including alternating layers of the first metal oxide layer and the second metal oxide layer, wherein the laminated film includes from about 5 pairs to about 200 pairs of the first metal oxide layer and the second metal oxide layer.

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

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

4. The method of claim 1, 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 laminated film has a thickness of about 5 nm to about 50 nm.

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

6. The method of claim 1, wherein: 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; and The substrate is exposed to the first metal alkoxide precursor for a period of about 0.1 second to about 10 seconds and exposed to the first purge gas for a period of about 1 second to about 120 seconds.

7. The method of claim 1, wherein: 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; and The substrate is exposed to the second metal alkoxide precursor for a period of about 0.1 second to about 10 seconds and exposed to the second purge gas for a period of about 1 second to about 120 seconds.

8. The method according to claim 1, 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.

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

10. The method according to claim 1, wherein the first metal alkoxide precursor and the second metal alkoxide precursor each independently comprise titanium(IV) n-propoxide, titanium(IV) isopropoxide, titanium(IV) n-butoxide, titanium(IV) tert-butoxide, hafnium(IV) n-propoxide, hafnium(IV) isopropoxide, hafnium(IV) n-butoxide, hafnium(IV) tert-butoxide, zirconium(IV) n-propoxide, zirconium(IV) isopropoxide, zirconium(IV) n-butoxide, zirconium(IV) tert-butoxide, aluminum(III) n-propoxide, aluminum(III) isopropoxide, aluminum(III) n-butoxide, aluminum(III) tert-butoxide, lanthanum(III) n-propoxide, lanthanum(III) isopropoxide, lanthanum(III) n-butoxide, lanthanum(III) tert-butoxide, isomers of the foregoing, or any combination of the foregoing.

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

12. The method according to claim 1, wherein: the first metal oxide layer comprises a first metal and the second metal oxide layer comprises a second metal; and the laminated film has an atomic ratio of the first metal to the second metal of about 5:1 to about 15:

1.

13. The method according to claim 1, wherein the passivated surface is capped with one or more alkyl groups.

14. The method according to 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 according to 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. A method of forming a metal oxide material, comprising: positioning a substrate in a processing chamber, wherein the substrate comprises a passivated surface and an unpassivated surface, and wherein the unpassivated surface is capped with a hydride group, a hydroxide group, or a combination of the foregoing; and selectively depositing a laminated film on the unpassivated surface while the passivated surface remains at least substantially free of the laminated film, wherein: the laminated film comprises two or more pairs of alternating layers of a first metal oxide layer and a second metal oxide layer; the first metal oxide layer and the second metal oxide layer each independently have a thickness of about 0.05 nm to about 10 nm; a first metal alkoxide precursor is thermally decomposed during a first pulsed chemical vapor deposition process to produce the first metal oxide layer; a second metal alkoxide precursor is 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 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; and The first temperature and the second temperature are each independently from about 150 °C to about 450 °C.

17. The method according to 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. The method according to claim 17, wherein the first temperature and the second temperature are each independently from about 200 °C to about 350 °C.

19. The method according to claim 16, wherein: The first metal oxide layer and the second metal oxide layer each independently have a thickness of about 0.1 nm to about 5 nm; and The laminated film comprises about 10 pairs to about 50 pairs of the first metal oxide layer and the second metal oxide layer.

20. A method of forming a metal oxide material, comprising: Positioning a substrate in a processing chamber, wherein the substrate comprises a passivated surface and an unpassivated surface, and wherein the unpassivated surface is capped with a hydride group, a hydroxide group, or a combination of the foregoing; Exposing the substrate to a first metal alkoxide precursor to produce a first metal oxide layer over or on the unpassivated surface, while the passivated surface remains 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 when 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, wherein the second metal alkoxide precursor is thermally decomposed to produce the second metal oxide layer when the substrate is maintained at a second temperature of about 150 °C to about 350 °C; and Sequentially repeating exposing the substrate to the first metal alkoxide precursor and the second metal alkoxide precursor to produce a laminated film comprising alternating layers of the first metal oxide layer and the second metal oxide layer, wherein the laminated film is amorphous, and wherein the laminated film comprises about 10 pairs to about 100 pairs of the first metal oxide layer and the second metal oxide layer, wherein: The first metal oxide layer and the second metal oxide layer each independently have about a thickness of 0.05 nm to about 10 nm; and The first metal oxide layer and the second metal oxide layer contain different metal oxides.

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