Selective deposition method

Abstract

A selective deposition method is disclosed. The selective deposition method includes providing a plurality of substrates in a processing chamber, the plurality of substrates having a first surface comprising a first material and a second surface comprising a second material, the first surface being different from the second surface, and selectively forming a layer comprising a metal on the first surface relative to the second surface, selectively forming the layer comprises: i) contacting the plurality of substrates with a precursor comprising a compound in the form of MXnOm, wherein: M is a metal; x is selected from F, Cl, Br and I; n and m are integers; n + 2m is at least 4 to at most 6; and ii) contacting the plurality of substrates with a reactant wherein step i) comprises pulsing the precursor at a pulse duration greater than 10 seconds.

Description

Technical Field

[0001] This disclosure generally relates to methods for depositing materials on a substrate. More specifically, this disclosure relates to selectively depositing materials on a first surface of a substrate relative to a second surface. Background Technology

[0002] Integrated circuits are manufactured through a fine process in which various material layers are deposited on a semiconductor substrate in a predetermined arrangement. This predetermined arrangement of materials on the semiconductor substrate can typically be achieved by depositing material across the entire substrate surface and then removing it from predetermined areas of the substrate, for example, through the deposition of a mask layer and subsequent etching. The material can be conductive to provide electrical connections within the integrated circuit.

[0003] Fabricating integrated surfaces on a substrate involves a large number of steps, making the manufacturing process very complex. The number of steps can be reduced by utilizing selective deposition processes, whereby material is selectively deposited on a first surface relative to a second surface, eliminating or minimizing the need for subsequent processing.

[0004] The throughput of integrated circuit manufacturing processes can be improved by simultaneously processing many substrates in a single reactor (e.g., a batch reactor or a vertical furnace). However, processes used in single-wafer reactors may not be easily converted to batch reactors due to very different process conditions, such as gas flow behavior, temperature variations, and required precursor quantities. Therefore, selective deposition processes capable of being performed simultaneously on multiple substrates are needed. Summary of the Invention

[0005] According to a first embodiment of the present invention, a selective deposition method is provided, comprising: providing a plurality of substrates in a processing chamber, the plurality of substrates having a first surface comprising a first material and a second surface comprising a second material, the first surface being different from the second surface, and selectively forming a layer comprising a metal on the first surface relative to the second surface, wherein selectively forming the layer comprises: i) subjecting the plurality of substrates to a layer comprising a metal in the form of MX n O m The precursor contact of the compound, wherein: M is a metal; X is selected from F, Cl, Br and I; n and m are integers; n+2m is at least 4 to at most 6; and ii) contacting multiple substrates with the reactant, wherein step i) includes pulse the precursor with a pulse duration of greater than 10 seconds.

[0006] Each of the multiple substrates may have a first surface and a second surface.

[0007] The metal contained in the precursor can be one of a transition metal, a post-transition metal, or a rare earth metal. The metal contained in the precursor can be molybdenum. The precursor may include a molybdenum tetrachloride precursor. The molybdenum tetrachloride precursor may include at least one of the following: molybdenum trichloride (V) (MoOCl3), molybdenum tetrachloride (VI) (MoOCl4), or molybdenum dichloride (IV) (MoO2Cl2).

[0008] Selective layer formation may include forming a first layer on a first surface and forming a second layer on a second surface, the second layer being at least twice as thick as the first layer.

[0009] Selective layer formation may include forming a first layer on a first surface and forming a second layer on a second surface, the second layer being at least five times thicker than the first layer.

[0010] Selective layer formation may include forming a first layer on a first surface and forming a second layer on a second surface, the second layer being at least ten times thicker than the first layer.

[0011] The reactants may contain hydrogen. The reactants may contain ammonia.

[0012] The method may include sequentially repeating steps i) and ii).

[0013] The method may include heating the substrate to a deposition temperature greater than 550°C. The method may also include heating the substrate to a deposition temperature greater than 600°C.

[0014] The primary material can be a metal. The primary material can be a metal nitride. The primary material can be a metal oxide.

[0015] The second material can be a dielectric material. The dielectric material can be silicon dioxide.

[0016] The pulse duration can be between 10 and 30 seconds. The pulse duration can be longer than 30 seconds. The pulse duration can be longer than 2 minutes. The pulse duration can be longer than 4 minutes.

[0017] During step i), the precursor may have a partial pressure of at least 1 Torr in the processing chamber. During step i), the precursor may have a partial pressure of at least 5 Torr in the processing chamber. During step i), the precursor may have a partial pressure of at least 10 Torr in the processing chamber.

[0018] Multiple substrates may include a third surface, which includes a third material different from the first material and the second material, and selectively forming layers may include selectively forming layers on the first surface and the third surface relative to the second surface.

[0019] Multiple substrates may include a third surface, which includes a third material different from the first material and the second material, wherein selectively forming a layer includes selectively forming a layer on the first surface relative to the second surface and the third surface.

[0020] The first material can be a metal or a metal nitride, the second material can be a dielectric material, and the third material can be a metal oxide.

[0021] The method may also include depositing a seed layer by repeating steps i) and ii).

[0022] The reactants may include ammonia. The method may also include contacting multiple substrates with a hydrogen purge gas after at least one repetition of steps i) and ii).

[0023] The method may include depositing a molybdenum host layer on the seed layer after depositing a seed layer.

[0024] According to a second aspect of the present invention, a semiconductor processing apparatus is provided, comprising a processing chamber for receiving a plurality of substrates supported on a substrate boat, at least one gas inlet for supplying gas to the processing chamber, a gas outlet for removing gas from the processing chamber, a precursor gas supply, a reactant gas supply, and a controller configured to execute a set of instructions to perform the following steps:

[0025] i) Make multiple substrates and contain MX-shaped components n O m The precursor contact of the compound, wherein: M is a metal; X is selected from F, Cl, Br and I; n and m are integers; n+2m is at least 4 to at most 6; and ii) contacting multiple substrates with the reactant, wherein step i) includes pulse the precursor with a pulse duration of greater than 10 seconds.

[0026] This summary is provided to present the chosen concepts in a simplified form. These concepts are further described in detail in the following description of exemplary embodiments of this disclosure. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter. Attached Figure Description

[0027] Specific embodiments of the invention will now be described by way of example with reference to the accompanying drawings, in which:

[0028] Figures 1a to 1d It is a schematic plan view of a substrate having first and second surfaces;

[0029] Figure 1e It is a schematic plan view of a substrate having a first, second, and third surface;

[0030] Figure 2aThis is a flowchart of a method according to an embodiment of the present invention;

[0031] Figure 2b This is a flowchart of another method according to an embodiment of the present invention;

[0032] Figure 3a The X-ray diffraction spectrum of the silicon substrate coated with alumina after undergoing a selective deposition method according to an embodiment of the present invention is shown; no molybdenum was detected. Similarly, the X-ray diffraction spectrum of the silicon substrate coated with silica after undergoing the same selective deposition method shows the absence of molybdenum.

[0033] Figure 3b The X-ray diffraction spectrum of a silicon substrate coated with molybdenum nitride after undergoing a selective deposition method according to an embodiment of the present invention; the presence of molybdenum was detected;

[0034] Figure 3c XPS analysis of a molybdenum nitride-coated substrate after undergoing a selective deposition method according to an embodiment of the invention is shown;

[0035] Figure 4 This is a schematic diagram of a substrate processing apparatus according to an embodiment of the present invention.

[0036] It should be understood that the elements in the accompanying drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements in the drawings may be exaggerated relative to other elements to help improve the understanding of the embodiments illustrated in this disclosure. Detailed Implementation

[0037] Although certain embodiments and examples are disclosed below, those skilled in the art will understand that the invention extends beyond the specific disclosed embodiments and / or uses of the invention and their obvious modifications and equivalents. Therefore, it is intended that the scope of the disclosed invention should not be limited to the specific disclosed embodiments described below. The illustrations presented herein are not intended to be actual views of any particular material, structure, or device, but are merely idealized representations used to describe embodiments of this disclosure.

[0038] The specific embodiments shown and described are illustrative of the invention and its best mode, and are not intended to further limit the scope of aspects and embodiments in any way. In fact, for the sake of brevity, conventional manufacturing, connection, preparation, and other functional aspects of the system may not be described in detail. Furthermore, the connecting lines shown in the figures are intended to represent exemplary functional relationships and / or physical connections between various elements. Many alternative or additional functional relationships or physical connections may exist in the actual system, and / or may not exist in some embodiments.

[0039] It should be understood that the configurations and / or methods described herein are exemplary in nature, and these specific embodiments or examples should not be considered limiting, as many variations are possible. The particular routines or methods described herein may represent one or more of any number of processing strategies. Therefore, the various actions shown may be performed in the order shown, in a different order, or in some cases omitted.

[0040] The subject matter of this disclosure includes all novel and non-obvious combinations and sub-combinations of the various processes, systems and configurations disclosed herein, as well as any and all equivalents thereof.

[0041] As used herein, the terms "substrate" or "wafer" can refer to any one or more underlying materials on which devices, circuits, or films can be formed. The term "semiconductor device structure" can refer to any portion of a processed or partially processed semiconductor structure that includes or defines at least a portion of active or passive components of a semiconductor device to be formed on or in a semiconductor substrate. Semiconductor substrates can be processed in batches in a vertical furnace. An example of such processing is the deposition of various material layers on the substrate.

[0042] Integrated circuits are fabricated through a process in which various material layers are deposited on a semiconductor substrate in a predetermined arrangement order. Metal layers may be required as conductive layers in the semiconductor device to electrically connect some of these layers. By utilizing a selective deposition process, the number of steps involved in fabricating an integrated surface on the substrate can be reduced, whereby material is selectively deposited on a first surface relative to a second surface, without requiring or reducing the need for subsequent processing. It has been found that a method may be needed to selectively deposit conductive material on a first surface relative to a second surface to provide electrical connections.

[0043] Gaps created during the fabrication of features in integrated circuit devices can be filled with metallic material. Gaps can have a high aspect ratio because their depth is much greater than their width. Gaps can be provided by a series of material layers, for example, through etching. It may be necessary to provide conductive material within the gaps. Gaps can be filled more completely and uniformly by depositing material at the bottom of the gap rather than on its sidewalls, thus preventing the formation of gaps.

[0044] refer to Figures 1a to 1d The diagram illustrates a substrate 1 having a first surface 2 and a second surface 3. The first surface 2 comprises a first material, and the second surface 3 comprises a second material. The first material is different from the second material. The first surface 2 differs from the second surface 3 in that the first surface 2 may not overlap with the second surface 3. The substrate 1 may have a first side 4 and an opposing second side 5. (Reference) Figure 1aThe first surface 2 and the second surface 3 can both be disposed on the first side 4 and / or the second side 5. The first surface 2 can be disposed on the first side 4, and the second surface 3 can be disposed on the second side 5. Figure 1b The first surface 2 and the second surface 3 can be adjacent to each other. Figure 1a or spaced apart from each other ( Figure 1c The first surface 2 and the second surface 3 can each be configured as a series of unconnected regions; for example, the first surface 2 can intersect with the second surface 3. Figure 1d It should be understood that, within the scope of the present invention, various arrangements of the first surface 2 and the second surface 3 relative to each other are possible.

[0045] refer to Figure 2a According to an embodiment of the present invention, the method can be performed as follows. In step S1, a plurality of substrates 1 are disposed in a processing chamber. The plurality of substrates have a first surface comprising a first material and a second surface comprising a second material, the first surface being different from the second surface. In step S2, the plurality of substrates are subjected to processing with a substrate comprising an MX-shaped material. n O m The precursor contact of the compound, wherein M is a metal; X is selected from F, Cl, Br, and I; n and m are integers; and n+2m is at least 4 and at most 6. O is oxygen. Step S2 includes pulsating the precursor for a pulse duration of greater than 10 seconds. In step S3, multiple substrates 1 are contacted with the reactants. Steps S2 and S3 provide the selective formation of a metal-containing layer on a first surface 2 relative to a second surface 3.

[0046] In step S1, providing multiple substrates in the processing chamber may include providing a substrate carrier or boat supporting the multiple substrates in the processing chamber. The processing chamber is described in more detail below. The processing chamber may be the processing chamber of a batch reactor (e.g., a vertical furnace). The multiple substrates may include, for example, at least 50, at least 100, at least 150, at least 170 or more substrates. The multiple substrates may have undergone prior processing, such as deposition of multiple layers, etching, annealing, oxidation and / or other processes to form a structure on the multiple substrates. The multiple substrates may include semiconductor wafers, such as 200 mm, 300 mm or 450 mm wafers. The multiple substrates have a first surface and a second surface. In some embodiments, each substrate 1 has a first surface 2 and a second surface 3. In some embodiments, the first surface is the surface of a first (group) of substrates in the multiple substrates, and the second surface is the surface of a second (group) of substrates in the multiple substrates, the first (group) of substrates being different from the second (group) of substrates. The reference herein to selective deposition on a first surface relative to a second surface may refer to selective deposition on each first surface of each substrate in the multiple substrates relative to each second surface of a corresponding substrate in the multiple substrates. The selective deposition on a first surface relative to a second surface mentioned in this article can refer to the selective deposition on a first surface of a first substrate relative to a second (group) of substrates in a plurality of substrates.

[0047] refer to Figure 2b The selective deposition process of steps S2 and S3 can be repeated sequentially until the metal-containing layer formed on the first surface has the desired thickness. For example, the selective deposition process of steps S2 and S3 can be an atomic layer deposition process. Between steps S2 and S3, the processing chamber can be purged with a purge gas. After step S3, the processing chamber can be purged with a purge gas. The purge gas can be an inert gas, such as argon or helium. The purge gas can be supplied to the chamber for a duration between 30 seconds and 60 seconds. Other purge gases are possible for the duration provided.

[0048] The precursor in step S2 is provided as a pulse of duration T1, which is greater than 10 seconds. For example, in some embodiments, T1 may be at least 10 seconds, at least 20 seconds, or at least 30 seconds. In some embodiments, T1 may be between 10 and 30 seconds, between 30 seconds and one minute, between one and two minutes, between two and three minutes, or between three and four minutes. In some embodiments, T1 may be greater than one minute, for example, between one and two minutes, or between one and three minutes, or between one and four minutes. In some embodiments, T1 may be greater than two minutes, for example, between two and three minutes, or between two and four minutes. In some embodiments, T1 may be greater than four minutes, for example, between four and five minutes, between four and six minutes, between four and seven minutes, or between four and eight minutes. The reactant in step S3 may be provided as a pulse of duration T2, which may be between 30 and 60 seconds. Other values ​​of T2 are possible, for example, less than 30 seconds or greater than 60 seconds.

[0049] Precursors include those in the form of MX n O m The compound. M is a metal, such as a transition metal, a post-transition metal, or a rare earth metal. The transition metal may be selected from molybdenum (Mo), tungsten (W), ruthenium (Ru), cobalt (Co), and copper (Cu). In some embodiments, the metal is selected as molybdenum, and the precursor includes molybdenum halide.

[0050] X is selected from F, Cl, Br, and I, i.e., halogens other than astatine and tennessine. In some embodiments, the metal is molybdenum and X is a chloride ion, thus forming a molybdenum oxychloride precursor. The precursor may include molybdenum trichloride (V) (MoOCl3), molybdenum tetrachloride (VI) (MoOCl4), or molybdenum dichloride (IV) (MoO2Cl2).

[0051] Reactants may include hydrogen, such as hydrogen gas (H2). Reactants may include ammonia (NH3).

[0052] The first material may include a metal, such as a transition metal. The transition metal may be selected from molybdenum, titanium (Ti), tantalum (Ta), manganese (Mn), tungsten (W), ruthenium (Ru), cobalt (Co), and copper (Cu). The first material may include a metal nitride. The first material may include a metal oxide.

[0053] The second material differs from the first material. The second material may include oxides, nitrides, or combinations thereof. Oxides, nitrides, or combinations thereof may be selected from alumina (AlOx), silicon oxide (SiOx), silicon nitride (SiN), hafnium oxide (HfO2), zirconium oxide (ZrO2), and silicon oxynitride (SiON). Silicon oxide may be a thermal oxide of silicon. Silicon oxide may be carbon-doped. The second material may be a dielectric material.

[0054] For example, in some embodiments, the first material may be alumina and the second material may be silicon dioxide. In some embodiments, the first material may be molybdenum or molybdenum nitride and the second material may be alumina. In some embodiments, the first material may be molybdenum or molybdenum nitride and the second material may be silicon dioxide.

[0055] Selectively forming a metal-containing layer on a first surface relative to a second surface can include forming a metal-containing layer on the first surface that is thicker than on the second surface. For example, a first metal-containing layer can be formed on the first surface, and a second metal-containing layer can be formed on the second surface, with the thickness of the first layer being at least twice the thickness of the second layer. Therefore, the first layer is selectively deposited relative to the second layer because the first layer is substantially thicker than the second layer. The first layer can be five or ten times thicker than the second layer. The first layer can be twenty times thicker than the second layer. In some embodiments, no layer or no detectable layer is deposited on the second surface. In some embodiments, the second layer has a thickness of less than 5 angstroms, less than 2 angstroms, or less than 1 angstrom.

[0056] In steps S2 and S3, multiple substrates can be heated to a temperature of at least 550°C. Heating can be provided by a processing chamber heater. Multiple substrates can be heated to a temperature of at least 600°C. Multiple substrates can be heated to a temperature of at least 550°C and less than 650°C. Multiple substrates can be heated to a temperature of at least 600°C and less than 700°C.

[0057] In step S2, the partial pressure of the precursor in the processing chamber can be controlled to a value of at least 1 Torr. In some embodiments, the partial pressure can be at least 5 Torr or at least 10 Torr. In some embodiments, the partial pressure can be between 1 Torr and 10 Torr, for example, between 1 Torr and 2 Torr, between 1 Torr and 2 Torr, between 2 Torr and 3 Torr, between 3 Torr and 4 Torr, between 4 Torr and 5 Torr, between 5 Torr and 6 Torr, between 6 Torr and 7 Torr, between 7 Torr and 8 Torr, between 8 Torr and 9 Torr, or between 9 Torr and 10 Torr. In some embodiments, the partial pressure can be greater than 10 Torr, for example, between 10 Torr and 11 Torr, between 11 Torr and 12 Torr, between 12 Torr and 13 Torr, between 13 Torr and 14 Torr, or between 14 Torr and 15 Torr. In some embodiments, the partial pressure can be between 0.5 Torr and 1 Torr, for example, between 0.5 Torr and 0.6 Torr, between 0.6 Torr and 0.7 Torr, between 0.7 Torr and 0.8 Torr, between 0.8 Torr and 0.9 Torr, or between 0.9 Torr and 1 Torr. The partial pressure can be selected according to the desired selectivity. In some embodiments, a small amount of inert gas (such as argon) can co-flow with the precursor, which helps prevent the precursor from diffusing back into the gas line upstream of the processing chamber. For example, the gas supplied to the processing chamber in step S2 may include 90% precursor and 10% argon (or other inert gas), or 95% precursor and 5% argon (or other inert gas).

[0058] refer to Figure 1e In some embodiments, a plurality of substrates 1 include a third surface 6, which comprises a third material different from the first and second materials. In some embodiments, the third surface 6 may be included in each of the plurality of substrates 1. In some embodiments, the third surface 6 may be included in a third (group) of substrates, which is different from the first (group) of substrates including the first surface and the second (group) of substrates including the second surface. The third surface 6 may be different from the first surface 2 and the second surface 3, i.e., the first surface 6 may not overlap with the first surface 2 and the second surface 3. The first surface 2 and the third surface 6 may be disposed on a first side 4 of the substrate 1, and the second surface 3 may be disposed on a second side 5 of the substrate 1. The first surface 2 and the second surface 3 may be disposed on the first side 4 of the substrate 1, and the third surface 6 may be disposed on the second side 5 of the substrate 1. The second surface 3 and the third surface 6 may be disposed on the first side 4, and the first surface 2 may be disposed on the second side 5. The first surface 2, the second surface 3, and the third surface 6 may each be disposed on the first side 4 and / or the second side 5. The first, second, and third surfaces 2, 3, and 6 may be adjacent to each other or spaced apart from each other. The first, second, and third surfaces 2, 3, and 6 can each be configured as a series of unconnected regions; for example, one or more of surfaces 2, 3, and 6 may intersect with one or more of surfaces 2, 3, and 6. It should be understood that various arrangements of the first, second, and third surfaces 2, 3, and 6 relative to each other are possible within the scope of this invention.

[0059] The third material can be a metal oxide, such as aluminum oxide or hafnium dioxide. The third material can also be a metal nitride, such as titanium nitride or vanadium nitride.

[0060] In some embodiments, the method includes selectively forming metal-containing layers on a first surface 2 and a third surface 10 relative to a second surface 3. Selectively forming metal-containing layers on the first surface 2 and the third surface 10 relative to the second surface 3 may include forming layers on the first surface 2 and the third surface 10 that are thicker than those on the second surface 3. For example, a first metal-containing layer may be formed on the first surface, a second metal-containing layer may be formed on the second surface, and a third metal-containing layer may be formed on the third surface. The thickness of the first layer may be at least twice the thickness of the second layer. The thickness of the third layer may be at least twice the thickness of the second layer. Therefore, the first and third layers are selectively deposited relative to the second layer because the first and third layers are substantially thicker than the second layer. The first layer may be five or ten times thicker than the second layer. The third layer may be five or ten times thicker than the second layer. The first layer may be twenty times thicker than the second layer. The third layer may be twenty times thicker than the second layer. The first and third layers do not necessarily have the same thickness. In some embodiments, no layer or no detectable layer is deposited on the second surface. In some embodiments, the second layer has a thickness of less than 5 angstroms, less than 2 angstroms, or less than 1 angstrom.

[0061] In some embodiments, the method includes selectively forming a metal-containing layer on a first surface 2 relative to the second surface 3 and the third surface 10. Selectively forming the metal-containing layer on the first surface 2 relative to the second surface 3 and the third surface 10 may include forming a layer on the first surface 2 that is thicker than that on the second surface 3 and the third surface 10. For example, a first metal-containing layer may be formed on the first surface, a second metal-containing layer may be formed on the second surface, and a third metal-containing layer may be formed on the third surface. The thickness of the first layer may be at least twice the thickness of the second layer. The thickness of the first layer may be at least twice the thickness of the third layer. Therefore, the first layer is selectively deposited relative to the second and third layers because the first layer is substantially thicker than the second and third layers. The first layer may be five or ten times thicker than the second layer. The first layer may be five or ten times thicker than the third layer. The first layer may be twenty times thicker than the second layer. The first layer may be twenty times thicker than the third layer. The second and third layers do not necessarily have the same thickness. In some embodiments, no layer or no detectable layer is deposited on the second surface. In some embodiments, the second layer has a thickness of less than 5 angstroms, less than 2 angstroms, or less than 1 angstrom. In some embodiments, no layer or no detectable layer is deposited on the third surface. In some embodiments, the third layer has a thickness of less than 5 angstroms, less than 2 angstroms, or less than 1 angstrom.

[0062] In some embodiments, the metal-containing layer may be a molybdenum layer. In some embodiments, the metal-containing layer may be a molybdenum nitride layer. In some embodiments, the metal-containing layer may be a molybdenum oxynitride layer.

[0063] In some embodiments, the first material may be a metal or a metal nitride, the second material may be a dielectric material, and the third material may be a metal oxide. For example, the first material may be molybdenum nitride, the second material may be silicon dioxide, and the third material may be aluminum oxide. Therefore, the method according to embodiments of the invention can provide selective deposition on a first surface containing a metal nitride (e.g., molybdenum nitride) relative to a second surface containing a dielectric (e.g., silicon dioxide) and a third surface containing a metal oxide (e.g., aluminum oxide). The method according to embodiments of the invention can provide selective deposition on a first surface containing a metal nitride (e.g., molybdenum nitride) and a third surface containing a metal oxide (e.g., aluminum oxide) relative to a second surface containing a dielectric (e.g., silicon dioxide).

[0064] In some embodiments, the precursor comprises molybdenum oxychloride and the reactant comprises ammonia. The selectively deposited metal-containing layer is molybdenum oxynitride (MoON). The MoON layer may remain as MoON or may be converted to MoN by contacting multiple substrates with hydrogen after at least one repetition of steps S2 and S3. In some embodiments, the first material may be alumina, the second material may be silicon dioxide, and MoON may be selectively deposited on alumina instead of silicon dioxide.

[0065] In some embodiments, a thin seed layer of MoON can be selectively deposited on alumina. Subsequently, a molybdenum host layer can be selectively deposited on the seed layer, for example, using a method according to embodiments of the invention. The deposition process for the host layer may include repeating steps S2 and S3 M times, where M is selected between 5 and 2000, preferably between 100 and 500, more preferably between 300 and 400. The host layer can have a thickness between 1 nm and 700 nm on a first surface of the substrate, preferably between 5 nm and 500 nm, more preferably between 50 nm and 300 nm. Optionally, a purging step that contacts multiple substrates with hydrogen can be performed prior to the deposition of the molybdenum host layer to reduce the oxygen content of the MoON layer. The use of a MoON seed layer is particularly advantageous in applications where the deposition of molybdenum on alumina (or other materials) is challenging.

[0066] The selective deposition process according to an embodiment of the invention is performed in a SONORA® vertical batch furnace (available from ASM International NV, Netherlands). Substrates (including silicon substrates coated with alumina, silicon substrates coated with silica, and silicon substrates coated with molybdenum nitride) are provided in the processing chamber of the vertical furnace. The precursor is molybdenum dichloride dioxide, and the reactant is ammonia. The precursor pulse duration is 4 minutes, and the precursor partial pressure is 10 Torr. The precursor and reactant are alternately provided to the processing chamber 150 times at a substrate temperature of 600°C. X-ray photoelectron spectroscopy (XPS) analysis is performed on each substrate. X-ray diffraction (XRD) analysis is performed on each substrate. In the X-ray diffraction analysis, no detectable amount of molybdenum was found on either the alumina- or silica-coated substrates. Figure 3a Clear MoO2+Mo2N diffraction peaks were observed on the molybdenum nitride-coated substrate. Figure 3b Metal-coated substrates Figure 3c The XPS analysis shown indicates that 270 nm of Mo2O was deposited. x N y layer.

[0067] refer to Figure 4 A semiconductor processing apparatus 100 according to an embodiment of the present invention is shown, wherein a selective deposition method as described herein can be performed. The apparatus includes a processing chamber 101 for receiving a plurality of substrates 1, 102 supported on a substrate carrier or boat 103, at least one gas inlet 104 (through which gas can be supplied to the processing chamber 101), a gas outlet 105 (through which gas can be removed from the processing chamber 101), a precursor gas supply 106, a reactant gas supply 107, and a controller 108.

[0068] The processing chamber 101 may be generally bell-shaped and may extend in a longitudinal direction, which may be horizontal or vertically aligned. The processing chamber 101 may have an open end 109 and a closed end 110. The substrate carrier 103 may be inserted into the processing chamber 101 through the open end 109. The open end 109 may be closed by a door 111.

[0069] The apparatus 100 may include one or more gas injectors 112 connected to a gas inlet 104 for supplying one or more gases into the interior of the processing chamber 101. The one or more gas injectors 112 may be dump injectors, multi-hole injectors, or other injector types. The gas inlet 104 may be connected to one or more gas lines 113 for supplying gas to the processing chamber 101. The one or more gas lines 113 may include a first gas line 1131 for supplying precursor gas from a precursor gas supply 106, a second gas line 1132 for supplying reactant gas from a reactant gas supply 107, and a third gas line 1134 for supplying purge gas from a purge gas supply 114. One or more of the precursor gas supply 106, reactant gas supply 107, and purge gas supply 114 may be connected to a corresponding subplant source (not shown). The apparatus 1 may include one or more exhaust lines 115 connected to a gas outlet 105 for removing gas from the interior of the processing chamber 101. The exhaust lines 115 may be connected to a vacuum pump 116. One or more flow controllers 116 may be provided in gas lines 113, 115 to control the flow rate of gas entering / leaving processing chamber 101 and thus control the pressure in processing chamber 101. Flow controllers 116 may include one or more of, for example, valves, mass flow controllers, and pressure control valves.

[0070] The apparatus 100 may include a heating element 117 for heating the processing chamber 101. The apparatus 100 may include one or more temperature sensors 118, such as thermocouples, in the processing chamber 101 for measuring the temperature within the processing chamber 101. The apparatus 100 may include one or more pressure sensors 119 in the processing chamber 101 for measuring the pressure within the processing chamber. The controller 108 may be configured to control, for example, the heating element 117 (thereby controlling the temperature of the substrate 102 in the processing chamber 101) and a valve / mass flow controller 116 (thereby controlling the type, pressure, and timing of the gas supplied to the processing chamber 101).

[0071] Controller 108 may be implemented in hardware or software. Controller 108 may be part of a central control module (not shown) (physically), or may be separate from and communicate with a central control module (not shown). Controller 108 may include a memory 120 configured to store instructions for performing methods according to embodiments of the present invention. Controller 108 may include a processor 121 configured to process and execute instructions loaded from memory 120. Controller 108 may include one or more inputs 122 for receiving data, signals, and / or instructions from elements included in the substrate processing apparatus 100, such as measurements of pressure, temperature, ozone concentration, etc., from pressure sensors, temperature sensors, ozone concentration sensors, etc. Controller 108 may include one or more outputs 123 for providing data, signals, and / or instructions to elements included in the substrate processing apparatus 100 (e.g., flow controller 116, heater 117) to control, for example, processing chamber pressure, precursor / reactant / purge gas pulse duration, and processing chamber temperature.

[0072] Although illustrative embodiments of the invention have been described above in part with reference to the accompanying drawings, it should be understood that the invention is not limited to these embodiments. By studying the drawings, the disclosure, and the appended claims, those skilled in the art will understand and implement variations of the disclosed embodiments in practicing the claimed invention.

[0073] The methods according to embodiments of the present invention are not limited to application in vertical furnaces or batch processing equipment, but can also be implemented in single-wafer or small-batch reactors.

[0074] Throughout this specification, references to "an embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment of the invention. Therefore, the phrases "in an embodiment" or "in one embodiment" appearing in various places throughout this specification do not necessarily refer to the same embodiment. Furthermore, it should be noted that specific features, structures, or characteristics of one or more embodiments can be combined in any suitable manner to form new, not explicitly described embodiments. The subject matter of this disclosure includes all novel and non-obvious combinations and sub-combinations of the various processes, systems, and configurations disclosed herein, as well as any and all equivalents thereof.

Claims

1. A selective deposition method, comprising: Multiple substrates are provided in a processing chamber. Each substrate has a first surface comprising a first material and a second surface comprising a second material, the first surface being different from the second surface. A metal-containing layer is selectively formed on the first surface relative to the second surface. The selectively formed layers include: i) Make multiple substrates and contain MX-shaped components n O m The precursor contact of the compound, wherein: M is a metal; X is selected from F, Cl, Br, and I; n and m are integers; n+2m is at least 4 and at most 6; and ii) Contact multiple substrates with the reactants. Step i) includes a pulse precursor with a pulse duration of more than 10 seconds.

2. The method according to claim 1, wherein, Each of the plurality of substrates has a first surface and a second surface.

3. The method according to claim 1 or 2, wherein, The metal contained in the precursor is one of the following: transition metal, post-transition metal, or rare earth metal.

4. The method according to any one of claims 1 to 3, wherein, The metal contained in the precursor is molybdenum.

5. The method according to claim 3, wherein, The precursor includes a molybdenum tetrachloride precursor, wherein the molybdenum tetrachloride precursor includes at least one of the following: molybdenum trichloride (V) (MoOCl3), molybdenum tetrachloride (VI) (MoOCl4), or molybdenum dichloride (IV) (MoO2Cl2).

6. The method according to any of the preceding claims, wherein, Selectively forming layers includes forming a first layer on the first surface and forming a second layer on the second surface, wherein the second layer is at least twice as thick as the first layer.

7. The method according to any of the preceding claims, wherein, The reactants contain hydrogen.

8. The method according to any of the preceding claims, wherein, The reactants include ammonia.

9. The method according to any of the preceding claims, comprising sequentially repeating steps i) and ii).

10. The method according to any of the preceding claims further comprises heating the substrate to a deposition temperature greater than 550°C.

11. The method according to any of the preceding claims, wherein, The first material is a metal.

12. The method according to any of the preceding claims, wherein, The first material is a metal nitride.

13. The method according to any of the preceding claims, wherein, The first material is a metal oxide.

14. The method according to any of the preceding claims, wherein, The second material is silicon dioxide.

15. The method according to any of the preceding claims, wherein, The duration of the pulse is between 10 and 30 seconds.

16. The method according to any of the preceding claims, wherein, The pulse duration is greater than 30 seconds.

17. The method according to any of the preceding claims, wherein, The precursor has a partial pressure of at least 5 Torr in the processing chamber during step i).

18. The method according to any of the preceding claims, wherein, The precursor has a partial pressure of at least 10 Torr in the processing chamber during step i).

19. The method according to any of the preceding claims further comprises depositing a seed layer by repeating steps i) and ii).

20. A semiconductor processing apparatus comprising a processing chamber for receiving a plurality of substrates supported on a substrate boat, at least one gas inlet for supplying gas to the processing chamber, a gas outlet for removing gas from the processing chamber, a precursor gas supply, a reactant gas supply, and a controller configured to execute a set of instructions to perform the following steps: i) Make multiple substrates and contain MX-shaped components n O m The precursor contact of the compound, wherein: M is a metal; X is selected from F, Cl, Br, and I; n and m are integers; n+2m is at least 4 and at most 6; and ii) Contact multiple substrates with the reactants. Step i) includes a pulse precursor with a pulse duration of more than 10 seconds.

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