Method and apparatus for filling gaps

Abstract

The invention relates to a method and apparatus for filling a gap. More specifically, the disclosed methods and systems perform one or more deposition cycles and radical treatments. Optionally, the methods and systems perform thermal annealing and vacuum ultraviolet radiation.

Description

Technical Field

[0001] The present disclosure generally relates to methods and apparatuses for semiconductor manufacturing. Background Art

[0002] The miniaturization of semiconductor devices has increased the speed and density of integrated circuits. However, due to the scaled geometries, it has become difficult to fill the gaps in the substrate with high-quality materials without any voids for shallow trench isolation, interlayer dielectrics, and passivation layers. Summary of the Invention

[0003] The Summary of the Invention is provided to introduce a selection of concepts in a simplified form. These concepts are further described in detail in the detailed description of the exemplary embodiments of the present disclosure below. The Summary of the Invention is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0004] Various embodiments of the present disclosure relate to methods that can be used to fill gaps on a substrate. While the ways in which various embodiments of the present invention address the disadvantages of existing methods are discussed in more detail below, generally speaking, various embodiments of the present invention provide improved methods for filling gaps on a substrate and improved reactor systems for filling gaps on a substrate. As explained in more detail below, using a multi-chamber reactor system and corresponding methods can reduce contamination associated with material deposition, can provide deposition materials with desired properties, and / or can increase the yield associated with the deposition of materials with desired properties and / or characteristics.

[0005] According to at least one embodiment of the present invention, a method for filling a gap with a material including silicon and nitrogen is provided. The method includes the steps of: providing a substrate into a reaction chamber, wherein the substrate includes at least one gap; depositing a material including silicon and nitrogen into the gap; and treating the deposited material with radical treatment.

[0006] In some embodiments, the deposition step is performed in a deposition reaction chamber, and the radical treatment step is performed in a radical treatment chamber; and the deposition reaction chamber and the radical treatment chamber are operatively coupled to allow the substrate to be transferred between them without any air interruption.

[0007] In some embodiments, the deposited material further includes carbon.

[0008] In some embodiments, the deposition step includes performing at least one deposition cycle. One deposition cycle includes providing a silicon precursor in a gas phase into the reaction chamber; and providing deposition plasma power to form activated species from the reactants. In some embodiments, the reactants include nitrogen gas. In some embodiments, the reactants include nitrogen gas and argon gas.

[0009] In some exemplary embodiments of the deposition step, a silicon precursor is provided into a reaction chamber to deposit a layer onto a substrate that includes at least one gap. In some embodiments, the deposited layer includes silicon and nitrogen. Additionally, a plasma pulse is provided, which includes exposing the substrate to plasma treatment.

[0010] In some embodiments, the silicon precursor can be any precursor containing silicon. In some embodiments, the silicon precursor includes an aminosilane or a silazane. In some embodiments, the silicon precursor is selected from bis(diethylamino)silane, diisopropylaminosilane, N-(diethylaminosilyl)-N-ethylethylamine, N,N'-dimethylsilylsilanediamine, hexamethyldisilazane, hexamethyltrisilazane, tetramethyldivinyldisilazane, tetramethyldisilazane, and tetraisocyanatosilane.

[0011] In some embodiments, the radical treatment includes generating a remote plasma; obtaining a radical stream from the remote plasma; and exposing the substrate to the radical stream. In some embodiments, the remote plasma source is an inductively coupled plasma. In some embodiments, an ion trap is used to obtain the radical stream from the remote plasma. In some embodiments, the ion trap is disposed in the reaction chamber between the remote plasma discharge and the substrate. In some embodiments, the ion trap is an electrically grounded grid. In some embodiments, the remote plasma discharge is generated by gas phase ionization of a gas having a radio frequency (RF) power of 6000 W or less. In some embodiments, the remote plasma discharge is generated by gas phase ionization of a gas having a radio frequency (RF) power of 2000 W or less. In some embodiments, the radical stream includes hydrogen radicals. In some embodiments, the remote plasma discharge is generated by gas phase ionization of a gas having a radio frequency (RF) power of 1000 W or less. In some embodiments, the remote plasma discharge is generated by gas phase ionization of a gas having a radio frequency (RF) power of 600 W or less. In some embodiments, the radical stream includes hydrogen radicals.

[0012] In some embodiments, the method further includes a thermal curing step between the deposition step and the treatment step. In some embodiments, the thermal curing step is performed in a thermal curing chamber that is operably coupled to the deposition reaction chamber and the radical treatment chamber to allow the substrate to be transferred between them without any air interruption.

[0013] In some embodiments, the thermal curing step includes treating the deposited material at a temperature between 400 °C and 600 °C.

[0014] In some embodiments, the method further includes a step of exposing the deposited material to vacuum ultraviolet radiation.

[0015] In some embodiments, the deposited material is subjected to vacuum ultraviolet radiation in a vacuum ultraviolet radiation chamber, which is operatively coupled to a deposition reaction chamber, a radical treatment chamber, and a thermal curing chamber to allow the substrate to be transferred between them without any air interruption.

[0016] In some embodiments, the wavelength of the vacuum ultraviolet radiation is 100 - 450 nm. In some embodiments, the wavelength of the vacuum ultraviolet radiation is 172 nm.

[0017] According to some embodiments of the present disclosure, a multi-chamber reactor system is provided. The system includes: a first reaction chamber configured to deposit a material containing silicon and nitrogen into the gaps on a substrate to form a deposited material; a second reaction chamber for treating the deposited material with radical treatment; and a controller. The controller is configured to provide a substrate including at least one gap into the first reaction chamber; perform a deposition cycle in the first reaction chamber; move the substrate to the second reaction chamber; and perform a radical treatment process in the second reaction chamber.

[0018] In some embodiments, the controller is configured to perform a plurality of deposition cycles in the first reaction chamber before moving the substrate to the second reaction chamber.

[0019] In some embodiments, the controller is further configured to move the substrate from the second reaction chamber to the first reaction chamber.

[0020] In some embodiments, the system further includes a third reaction chamber for thermally curing the substrate, wherein the controller is configured to move the substrate to the third reaction chamber; and perform a curing process.

[0021] In some embodiments, the system further includes a fourth reaction chamber for exposing the substrate to vacuum ultraviolet radiation, wherein the controller is configured to move the substrate to the fourth reaction chamber; and perform an exposure process.

[0022] In some embodiments, the deposition cycle includes: pulsing a silicon precursor from a silicon precursor source into the first reaction chamber; and providing deposition plasma power to form active species from the reactants to deposit a material containing silicon and nitrogen.

[0023] In some embodiments, the ultraviolet light is provided by an excimer lamp.

[0024] In some embodiments, the ultraviolet light source is a low-pressure mercury lamp.

[0025] In some embodiments, the wavelength of the vacuum ultraviolet light is 100 - 450 nm.

[0026] In some embodiments, the wavelength of the vacuum ultraviolet light is 172 nm.

[0027] In some embodiments, the thermal annealing includes heating the substrate to a temperature between 400 °C and 600 °C.

[0028] In some embodiments, the radical treatment includes generating a remote plasma; obtaining a radical stream from the remote plasma; and exposing the substrate to the radical stream.

[0029] In some embodiments, an ion trap is used to obtain the radical stream from the remote plasma.

[0030] In some embodiments, the ion trap is disposed in the reaction chamber between the remote plasma discharge and the substrate.

[0031] In some embodiments, the ion trap is an electrically grounded grid plate.

[0032] In some embodiments, the remote plasma discharge is generated by gas phase ionization of a gas having a radio frequency (RF) power of 500 W or less.

[0033] In some embodiments, the remote plasma discharge is generated by gas phase ionization of a gas having a radio frequency (RF) power of 100 W or less.

[0034] In some embodiments, the radical stream contains hydrogen radicals.

[0035] These and other embodiments will become apparent to those skilled in the art from the following detailed description of certain embodiments with reference to the accompanying drawings. The invention is not limited to any particular embodiment disclosed. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] A more complete understanding of the exemplary embodiments of the present disclosure can be obtained by reference to the detailed description and the claims when considered in conjunction with the following illustrative drawings.

[0037] Figure 1 A multi-chamber reactor system according to at least one embodiment of the present disclosure is shown.

[0038] Figure 2 A method according to at least one embodiment of the present disclosure is shown.

[0039] Figure 3 A reaction chamber suitable for use according to an embodiment of the present disclosure is shown.

[0040] Figure 4 An example of an embodiment of a radical treatment chamber is shown.

[0041] It should be understood that the elements in the 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 illustrated embodiments of the present disclosure. Detailed implementation mode

[0042] Although certain embodiments and examples are disclosed below, those skilled in the art will understand that the present invention extends beyond the specifically disclosed embodiments and / or the uses of the present invention and its obvious modifications and equivalents. Therefore, it is intended that the scope of the disclosed invention should not be limited by the specific disclosed embodiments described below.

[0043] Exemplary embodiments of the present disclosure provide improved systems and methods for filling gaps on a substrate. The exemplary systems and methods can be used to fill gaps with materials including silicon and nitrogen. In addition, the exemplary systems and methods can be used to deposit, treat with radicals, and optionally expose to vacuum ultraviolet radiation, and thermally cure materials containing silicon and nitrogen. In some embodiments, all of these steps are completed in a single processing module, for example, without exposing the substrate to environmental conditions. Thus, any contamination of the surface that might otherwise occur due to performing pre - deposition processing and / or exposure to environmental conditions can be reduced or avoided.

[0044] In the present disclosure, "gas" can include materials that are gases at normal temperature and pressure (NTP), evaporated solids, and / or evaporated liquids, and can consist of a single gas or a gas mixture, depending on the context. Gases other than the processing gas (i.e., gases introduced without passing through a gas distribution component, a multi - port injection system, other gas distribution devices, etc.) can be used, for example, to seal the reaction space, and can include sealing gases, such as inert gases. In some cases, the term precursor can refer to a compound that participates in a chemical reaction to produce another compound, and particularly to a compound that constitutes the film matrix or the main framework of the film. In some cases, the term reactant can be used interchangeably with the term precursor. The term inert gas can refer to a gas that does not participate in a chemical reaction and / or does not become a part of the film matrix to an appreciable extent. Exemplary inert gases include He, Ar, H2, N2 (e.g., when not activated by plasma), and any combination thereof.

[0045] As used herein, the term "substrate" can refer to any one or more underlying materials that can be used to form or on which a device, circuit, or film can be formed. The substrate can comprise a bulk material, such as silicon (e.g., single - crystal silicon), and can comprise one or more layers overlying the bulk material. In addition, the substrate can include various topologies, such as recesses, lines, etc., formed within or on at least a portion of the layers of the substrate. For example, the substrate can include a surface comprising a first material and a second material, as described in more detail below.

[0046] As used herein, the term "deposited material, film, and / or layer" can refer to any continuous or discontinuous structure and material, such as a material deposited by a method disclosed herein. For example, the deposited material, film, and / or layer can include two-dimensional materials, three-dimensional materials, nanoparticles, or even partial or complete molecular layers or partial or complete atomic layers or atomic and / or molecular clusters. The film or layer can include a material or layer having pinholes, which can be at least partially continuous. Alternatively, the film or layer can consist entirely of isolated islands.

[0047] As used herein, the term "cyclic deposition" can refer to a process that includes sequentially introducing precursors and / or reactants into a reaction chamber and / or sequentially applying plasma power pulses to deposit a layer on a substrate. Cyclic deposition processes include processing techniques such as atomic layer deposition (ALD), cyclic chemical vapor deposition (CCVD), and plasma-enhanced ALD and CCVD.

[0048] As used herein, the term cyclic chemical vapor deposition can refer to any process in which a substrate is sequentially exposed to two or more volatile precursors / reactants that react and / or decompose on the substrate to produce a desired deposit.

[0049] As used herein, "plasma" refers to an ionized gas composed of approximately equal numbers of negatively and positively charged species (usually electrons and ions). The plasma also contains excited and reactive species, such as atoms and radicals, metastable atoms and molecules, and photons. Plasma discharge requires an externally applied electric or magnetic field to ionize the gas. Plasma generation schemes and geometries include, but are not limited to, microwave plasma, capacitively coupled plasma, inductively coupled plasma, and RF - hollow cathode (HC) plasma, which differ in the generation of their excited and reactive species and, thus, can provide very different fluxes of various species.

[0050] As used herein, a "direct plasma generator" can refer to an active species generator configured to form and maintain a plasma between a perforated panel of a showerhead injector and a substrate support of the processing chamber within the processing chamber, while a "remote plasma generator" can refer to an active species generator configured to form and maintain a plasma within the processing chamber such that an ion trap of the processing chamber is disposed between the plasma and the substrate support of the processing chamber. Additionally, a "remote plasma generator" can refer to an active species generator configured to form and maintain a plasma outside the processing chamber and introduce the active species formed in the plasma into the processing chamber, for example, via an active species conduit or channel.

[0051] Materials comprising silicon and nitrogen may include, consist of, or consist essentially of silicon nitride materials. Materials consisting of silicon nitride may include acceptable amounts of impurities such as carbon, chlorine or other halogens, and / or hydrogen, which may be derived from one or more precursors used to deposit the silicon nitride material. As used herein, SiN or silicon nitride refers to a compound comprising silicon and nitrogen. SiN may be represented as SiNx, where x varies, for example, from about 0.5 to about 2.0, where some Si-N bonds are formed. In some cases, x may vary from about 0.9 to about 1.7, from about 1.0 to about 1.5, or from about 1.2 to about 1.4. In some embodiments, silicon nitride is formed where Si has an oxidation state of +IV and the amount of nitride in the material may vary. Silicon nitride may include silicon carbonitride (SiCN), which includes silicon, carbon, and nitrogen.

[0052] In some embodiments, the materials comprising silicon and nitrogen further comprise carbon. These films include, consist of, or consist essentially of silicon carbonitride materials. Materials consisting of silicon carbonitride may include acceptable amounts of impurities such as chlorides or other halogens, and / or hydrogen, which may be derived from one or more precursors used to deposit the silicon carbonitride material. As used herein, SiCN or silicon carbonitride refers to a compound comprising silicon, carbon, and nitrogen.

[0053] As used herein, "structure" may include a substrate as described herein. The structure may include one or more layers covering the substrate, such as one or more layers formed according to the methods described herein.

[0054] Furthermore, in the present disclosure, any two numbers of a variable may constitute a workable range of the variable, and any range indicated may include or exclude the endpoints. Additionally, any value of a variable indicated (whether or not it is indicated with "about") may refer to an exact value or an approximate value and include equivalents, and may refer to an average value, a median value, a representative value, a majority value, etc. Moreover, in the present disclosure, the terms "comprising", "consisting of", and "having" may, in some embodiments, independently refer to "generally or broadly including", "containing", "consisting essentially of", or "consisting of". It should be understood that when a composition, method, device, etc. is said to include certain features, it means that it includes those features and it does not necessarily exclude the presence of other features, provided they do not render the claims unworkable. Nevertheless, the term "comprising" or "including" or "having" includes the meaning of "consisting of", i.e., the situation where the composition, method, device, etc. being discussed includes only the listed features, components, and / or steps and does not contain any other features, components, steps, etc., and includes "consisting essentially of".

[0055] In the present disclosure, the meaning of any definition may not necessarily exclude the ordinary and customary meaning in some embodiments.

[0056] According to at least one embodiment of the present invention, a method for filling gaps with a material comprising silicon and nitrogen is provided. The method includes the steps of: providing a substrate into a reaction chamber, wherein the substrate includes at least one gap; depositing a material comprising silicon and nitrogen; and treating the deposited material with a radical treatment. In some embodiments, the deposition step is performed in a deposition reaction chamber, and the radical treatment step is performed in a radical treatment chamber; and the deposition reaction chamber and the radical treatment chamber are operably coupled to allow the substrate to be transferred between them without any air interruption.

[0057] In some embodiments, the deposition step includes performing at least one deposition cycle. One deposition cycle includes providing a silicon precursor in a gas phase into the reaction chamber; and providing deposition plasma power to form activated species from reactants. In some embodiments, the reactants include nitrogen gas. In some embodiments, the reactants include nitrogen gas and argon gas.

[0058] According to some exemplary embodiments of the deposition step, a silicon precursor is provided into the reaction chamber to deposit a layer onto a substrate comprising at least one gap. In some embodiments, the deposited layer comprises silicon and nitrogen. Additionally, a plasma pulse is provided, which includes exposing the substrate to plasma treatment. The plasma treatment allows the deposited layer to polymerize and transform into a flowable film. Then, the flowable film will fill the gaps on the substrate without forming any voids. The plasma treatment includes generating a plasma using reactants (such as plasma gases). The plasma gases include at least nitrogen gas, and optionally include one or more noble gases. In some embodiments, the noble gas is argon or helium.

[0059] In some embodiments, the silicon precursor can be any precursor containing silicon. In some embodiments, the silicon precursor contains aminosilane or silazane. In some embodiments, the silicon precursor is selected from bis(diethylamino)silane, diisopropylaminosilane, N-(diethylaminosilyl)-N-ethylethylamine, N,N'-dimethylsilylsilanediamine, hexamethyldisilazane, hexamethytrisilazane, tetramethyldivinyldisilazane, tetramethyldisilazane, and tetraisocyanatosilane.

[0060] In some embodiments, the radical treatment includes generating a remote plasma; obtaining a radical stream from the remote plasma; and exposing a substrate to the radical stream. In some embodiments, the radical stream contains hydrogen radicals. Then, the radical stream reaches the surface of the substrate and reacts with the hydrogen atoms in the deposited material. As the amount of hydrogen atoms decreases, the wet etching rate ratio of the deposited material improves, in other words, the wet etching rate ratio decreases. The reduction of the wet etching rate ratio is about 70% lower compared to the material without radical treatment. In embodiments where the deposited material contains carbon, the radical stream reacts with the surface of the substrate such that the amount of carbon atoms in the film decreases. The amount of carbon atoms is reduced by at least 90% compared to the material without radical treatment.

[0061] In some embodiments, an ion trap is used to obtain a radical stream from the remote plasma. In some embodiments, the ion trap is disposed in the reaction chamber between the remote plasma discharge and the substrate. In some embodiments, the ion trap is an electrically grounded grid. In some embodiments, the remote plasma discharge is generated by gas phase ionization of a gas having a radio frequency (RF) power of 500 W or less. In some embodiments, the remote plasma discharge is generated by gas phase ionization of a gas having a radio frequency (RF) power of 100 W or less.

[0062] In some embodiments, the method further includes a thermal curing step between the deposition step and the treatment step. The thermal curing step improves some film properties of the deposited material. In some cases, thermal curing densifies the film. In some embodiments, the thermal curing step is performed in a thermal curing chamber that is operably coupled to the deposition reaction chamber and the radical treatment chamber to allow the substrate to be transferred between them without any air interruption. In some embodiments, the thermal curing step includes treating the deposited material at a temperature between 400 °C and 600 °C.

[0063] In some embodiments, the method further includes a step of exposing the deposited material to vacuum ultraviolet radiation. The vacuum ultraviolet radiation improves some film properties of the deposited material. In some cases, the vacuum ultraviolet radiation promotes crosslinking of the molecules in the film. In some embodiments, the deposited material is subjected to vacuum ultraviolet radiation in a vacuum ultraviolet radiation chamber that is operably coupled to the deposition reaction chamber, the radical treatment chamber, and the thermal curing chamber to allow the substrate to be transferred between them without any air interruption.

[0064] In some embodiments, the wavelength of the vacuum ultraviolet radiation is 100 - 450 nm. In some embodiments, the wavelength of the vacuum ultraviolet radiation is 172 nm.

[0065] According to at least some embodiments of the present disclosure, a multi-chamber reactor system is provided. The system includes a first reaction chamber configured to deposit a material containing silicon and nitrogen into gaps on a substrate to form a deposited material. The system further includes a second reaction chamber and a controller. The second reaction chamber is for treating the deposited material using radical treatment. The controller is configured to provide a substrate including at least one gap into the first reaction chamber, perform at least one deposition cycle in the first reaction chamber, move the substrate to the second reaction chamber, and perform a radical treatment process in the second reaction chamber.

[0066] In some embodiments, the controller is configured to perform a plurality of deposition cycles in the first reaction chamber before moving the substrate to the second reaction chamber. In some embodiments, the controller is further configured to move the substrate from the second reaction chamber to the first reaction chamber.

[0067] In some embodiments, the deposition cycle includes: pulsing a silicon precursor from a silicon precursor source into the first reaction chamber; and providing deposition plasma power to form an activated species from the reactants to deposit a material containing silicon and nitrogen.

[0068] In some embodiments, the radical treatment includes generating a remote plasma; obtaining a radical stream from the remote plasma; and exposing the substrate to the radical stream. In some embodiments, the radical stream contains hydrogen radicals.

[0069] In some embodiments, an ion trap is used to obtain the radical stream from the remote plasma. In some embodiments, the ion trap is disposed in the reaction chamber between the remote plasma discharge and the substrate. In some embodiments, the ion trap is an electrically grounded grid plate. In some embodiments, the remote plasma discharge is generated by gas phase ionization of a gas with a radio frequency (RF) power of 500 W or less. In some embodiments, the remote plasma discharge is generated by gas phase ionization of a gas with a radio frequency (RF) power of 100 W or less.

[0070] In some embodiments, the system further includes a third reaction chamber for thermally curing the substrate, wherein the controller is configured to move the substrate to the third reaction chamber; and perform a thermal curing process. In some embodiments, the thermal curing includes heating the substrate to a temperature between 400 and 600 °C.

[0071] In some embodiments, the controller is configured to move the substrate to the first chamber to perform a plurality of deposition cycles, then move the substrate from the first chamber to the third chamber to thermally cure the substrate, then move the substrate from the third chamber to the second chamber for radical treatment, and finally the substrate can be moved back to the first chamber to start a new cycle. Multiple such cycles can be performed in one process.

[0072] In some embodiments, the system further includes a fourth reaction chamber for exposing the substrate to vacuum ultraviolet radiation, wherein the controller is configured to move the substrate to the fourth reaction chamber; and perform the exposure process.

[0073] In some embodiments, the ultraviolet light is provided by an excimer lamp. In some embodiments, the ultraviolet light source is a low-pressure mercury lamp. In some embodiments, the wavelength of the vacuum ultraviolet light is 100 - 450 nm. In some embodiments, the wavelength of the vacuum ultraviolet light is 172 nm.

[0074] In some embodiments, the controller is configured to move the substrate to the first chamber to perform a plurality of deposition cycles, then move the substrate from the first chamber to the fourth chamber to expose the substrate to vacuum ultraviolet radiation, then move the substrate from the fourth chamber to the third chamber to thermally cure the substrate, then move the substrate from the third chamber to the second chamber for radical treatment, and finally the substrate can be moved back to the first chamber to start a new cycle. Multiple such cycles can be performed in one process.

[0075] Turning now to the drawings, Figure 1 A multi-chamber reactor system 100 according to an embodiment of the present disclosure is shown. In the example shown, the multi-chamber reactor system 100 includes a first reaction chamber RC1, a second reaction chamber RC2, a third reaction chamber RC3, and a fourth reaction chamber RC4. The configuration of RC1 - RC4 can vary according to the desired process. The following will be combined with Figure 3 Exemplary reaction chambers suitable for use as one or more of RC1 - RC4 will be described in more detail.

[0076] According to an example of the present disclosure, at least one of RC1 - RC4 is configured to deposit a material including silicon and nitrogen on the surface of the substrate. For example, RC1 can be configured to deposit a material including silicon and nitrogen on the surface of the substrate.

[0077] According to a further example of the present disclosure, at least one of RC1 - RC4 is configured to expose the deposited material to vacuum ultraviolet radiation. For example, RC2 can be configured to expose the deposited material to vacuum ultraviolet radiation.

[0078] According to a further example of the present disclosure, at least one of RC1 - RC4 is configured to cure the deposited material using thermal curing. For example, RC3 can be configured to cure the deposited material.

[0079] According to a further example of the present disclosure, at least one of RC1 - RC4 is configured to treat the deposited material with radical treatment. For example, RC4 can be configured to treat the deposited material with radical treatment.

[0080] The multi-chamber reactor system 100 may further include a substrate handler SH configured to move substrates between two or more reaction chambers RC1-RC4. For example, the substrate handler SH (and the controller 114) may be configured to move substrates between RC1, RC2, RC3, and RC4 and optionally repeat. Additionally or alternatively, the substrate handler SH (and the controller 114) may move substrates between RC1 and RC4 and repeat and / or move substrates between RC1, RC3, and RC4 and repeat.

[0081] The multi-chamber reactor system 100 may further include a silicon precursor source 102 coupled to RC1 and / or RC3. Each silicon precursor source 102, 104 includes a container and a silicon precursor therein. Exemplary suitable silicon precursors are set forth in the foregoing description. Although shown separately, the silicon precursor sources 102, 104 may be a single precursor source.

[0082] The controller 114 may be configured to move substrates within the multi-chamber reactor system 100 and implement deposition and processing procedures as described herein. By way of example, the controller 114 may be configured to provide a substrate in a first reaction chamber, perform a deposition cycle in the first reaction chamber, move the substrate to a second reaction chamber, and perform an exposure process in the second reaction chamber. As a specific example, the controller 114 may be configured to perform a deposition cycle in the first reaction chamber, wherein the deposition cycle includes pulsing a silicon precursor from the silicon precursor source 102 into the first reaction chamber RC1, providing a nitrogen-containing reactant from the nitrogen-containing reactant source 106 to the first reaction chamber RC1, and providing deposition plasma power to form an activated species from the nitrogen-containing reactant. Additionally or alternatively, the controller 114 may be configured to perform a vacuum ultraviolet radiation exposure process in the second reaction chamber RC2, wherein the exposure process includes providing vacuum ultraviolet radiation. Additionally or alternatively, the controller 114 may be configured to perform a thermal curing process in the third reaction chamber RC3, wherein the thermal process includes heating the reaction chamber to a temperature above 400 °C. Additionally or alternatively, the controller 114 may be configured to perform a radical treatment in the fourth reaction chamber RC4, wherein the substrate is exposed to a radical stream. According to examples of these embodiments, the controller 114 is configured to perform a plurality of deposition cycles (e.g., between about 1 and about 500 or between about 1 and 300) in the first reaction chamber RC1 before moving the substrate to the second reaction chamber RC2. In some cases, the controller is also configured to move the substrate from the second reaction chamber RC2 to the first reaction chamber RC1.

[0083] Turning now to the drawings, Figure 1Illustrates a multi-chamber reactor system 100 according to an embodiment of the present disclosure. In the illustrated example, the multi-chamber reactor system 100 includes a first reaction chamber RC1, a second reaction chamber RC2, a third reaction chamber RC3, and a fourth reaction chamber RC4. The configuration of RC1-RC4 can vary according to the desired process. The following is described in conjunction with Figure 3 Exemplary reaction chambers suitable for use as one or more of RC1-RC4 are described in more detail.

[0084] According to an example of the present disclosure, at least one of RC1-RC4 is configured to deposit a silicon-containing film on the surface of a substrate to form a deposited layer containing silicon oxide. For example, RC1 and RC3 can be configured to deposit a silicon-containing film on the surface of a substrate.

[0085] According to a further example of the present disclosure, at least one of RC1-RC4 is configured to expose the deposited layer to vacuum ultraviolet radiation. For example, RC2 and / or RC4 can be configured to process the deposited silicon nitride.

[0086] According to a further example of the present disclosure, at least one of RC1-RC4 is configured to process the exposed layer using thermal annealing. For example, RC2 and / or RC4 can be configured to process the deposited silicon nitride.

[0087] The multi-chamber reactor system 100 may further include a substrate handler SH configured to move a substrate between two or more reaction chambers RC1-RC4. For example, the substrate handler SH (and the controller 114) can be configured to move the substrate between RC1, RC2, RC3, and RC4 and optionally repeat. In these cases, the third reaction chamber RC3 can be configured to deposit an additional silicon-containing layer on the surface of the processed and / or exposed layer, and RC4 can be configured to process the silicon-containing layer. Additionally or alternatively, the substrate processor SH (and the controller 114) can move the substrate between RC1 and RC2 and repeat and / or move the substrate between RC3 and RC4 and repeat.

[0088] The multi-chamber reactor system 100 may further include a silicon precursor source 102 coupled to, for example, RC1. Each silicon precursor source 102 includes a container and a silicon precursor therein. Exemplary suitable silicon precursors are described below. Although shown separately, the silicon precursor source 102 can be a single precursor source.

[0089] The multi-chamber reactor system 100 may further include a hydrogen source 108 coupled to, for example, RC4. Each hydrogen source 108 includes a container and hydrogen therein.

[0090] The controller 114 can be configured to move substrates within the multi-chamber reactor system 100 and implement deposition and processing procedures as described herein. For example, the controller 114 can be configured to provide a substrate in a first reaction chamber, perform a deposition cycle in the first reaction chamber, move the substrate to a second reaction chamber, and perform an exposure process in the second reaction chamber.

[0091] As a specific example, the controller 114 can be configured to perform a deposition cycle in the first reaction chamber, where the deposition cycle includes pulsing a silicon precursor from the silicon precursor source 102 into the first reaction chamber RC1, providing a nitrogen-containing reactant from the nitrogen-containing reactant source 106 to the first reaction chamber RC1, and providing deposition plasma power to form an activated species from the nitrogen-containing reactant. According to examples of these embodiments, the controller 114 is configured to perform a plurality of deposition cycles (e.g., between about 1 and about 500 or between about 1 and 300) in the first reaction chamber RC1 before moving the substrate to the second reaction chamber RC2.

[0092] Additionally or alternatively, the controller 114 can be configured to perform an exposure process in the second reaction chamber RC2, where the exposure process includes providing a reactant from the reactant source 110 to the second reaction chamber RC2 and providing vacuum ultraviolet radiation to form an activated species from the reactant. In some embodiments, the reactant is selected from ammonia, argon, nitrogen, hydrogen, oxygen, and mixtures thereof.

[0093] According to a further example of the present disclosure, the controller 114 is further configured to ramp up the flow rate of the reactant from the reactant source 110 after the substrate is within the second reaction chamber. The controller 114 can be further configured to ramp down the flow rate of the reactant before removing the substrate from the second reaction chamber. One or both of the ramp rates can be relatively constant.

[0094] Additionally or alternatively, the controller 114 can be configured to perform an annealing process in the third reaction chamber RC3, where the annealing process includes heating the reaction chamber to a temperature above 400 °C.

[0095] Additionally or alternatively, the controller 114 can be configured to perform a radical treatment process in the fourth reaction chamber RC4, where the radical process includes exposing the substrate to a radical stream.

[0096] Figure 2 A method 200 for filling gaps with a material including silicon and nitrogen is shown according to additional embodiments of the present disclosure.

[0097] Method 200 includes the following steps: providing a substrate in a reaction chamber (step 202), depositing a material comprising silicon and nitrogen (step 204), optionally exposing the deposited material to vacuum ultraviolet (VUV) radiation (step 206), optionally treating the exposed material with a thermal curing step (step 208), and finally exposing the material to a radical treatment to form a silicon oxide-containing layer (step 210).

[0098] During step 202, the substrate is provided into the reaction chamber of the reactor. The substrate includes at least one gap. Optionally, the reactor including the reaction chamber can be provided with a heater to activate the reaction by raising the temperature of one or more of the substrate and / or reactants / precursors.

[0099] During step 202, the substrate can be brought to a desired temperature and pressure for step 204. For example, the temperature in the reaction chamber (such as the temperature of the substrate or the substrate support) can be between about 50 °C and about 200 °C or between about 80 °C and about 150 °C. The pressure in the reaction chamber can be about 0.5 Torr to about 50 Torr or about 1 Torr to about 30 Torr.

[0100] During step 204, one or more deposition cycles are performed to deposit a silicon- and nitrogen-containing material on the surface of the substrate. In some cases, the deposited silicon- and nitrogen-containing material is flowable. In some embodiments, the deposition process includes providing a silicon precursor. In some embodiments, the deposition process includes providing a silicon precursor and a plasma pulse. In some embodiments, the deposition process includes providing a silicon precursor, providing a second precursor, and a plasma pulse. In embodiments including a plasma pulse, the plasma polymerizes the deposited layer to make it flowable.

[0101] In one embodiment, the deposition cycle includes: pulsing a silicon precursor from a silicon precursor source into a first reaction chamber; and providing deposition plasma power to form an activated species from the reactants, thereby depositing a layer comprising silicon nitride.

[0102] During step 204, plasma power is provided for a plasma period to form an activated species from the reactant gas. The deposition plasma power can have a frequency between about 100 kHz and about 60 MHz and / or between about 12 MHz and about 14 MHz. For a 300 mm diameter substrate, the plasma power can have a power between about 10 W and about 2000 W or between about 100 W and about 900 W or be about 30 W to about 500 W, or have a similar power density for substrates of different cross-sectional sizes, and particularly for CCP processes. The power level for ICP processes can be higher. The duration of step 204 can be between about 0.05 seconds and about 60 seconds or between about 0.5 seconds and about 30 seconds.

[0103] In some embodiments, multiple deposition cycles are performed before moving the substrate to the second reaction chamber.

[0104] During optional step 206, the deposited layer is exposed to VUV radiation in the second reaction chamber. In some embodiments, the ultraviolet radiation is provided by an excimer lamp. In some embodiments, the ultraviolet radiation source is a low-pressure mercury lamp. In some embodiments, the wavelength of the vacuum ultraviolet light is 100 - 450 nm. In some embodiments, the wavelength of the vacuum ultraviolet light is 172 nm. After exposure step 206, the substrate is moved to the third reaction chamber for optional annealing step 208.

[0105] During optional step 208, the exposed layer undergoes an annealing step. In some embodiments, the annealing step includes thermal annealing, where the substrate is subjected to a temperature between 400 °C and 600 °C. In some embodiments, the substrate is subjected to a temperature of about 500 °C or about 550 °C. During step 208, the pressure inside the reaction chamber can be between about 1 Torr and about 30 Torr or between about 2.6 Torr and about 15 Torr.

[0106] Thermal annealing densifies the formed layer as it can reduce the number of Si - H bonds in the formed layer. After thermal annealing, the substrate can be moved to the fourth reaction chamber.

[0107] During step 210, the substrate is exposed to radical treatment. The radical treatment is performed by exposing the substrate to a radical stream. The radical stream is obtained from a remote plasma generated by a plasma unit. A radio frequency (RF) (e.g., 13.56 MHz or 27 MHz) plasma generator is used to generate the plasma by gas-phase ionization of a reactive gas. In some embodiments, the reactive gas contains hydrogen and optionally additionally contains nitrogen and / or oxygen. The plasma from the plasma unit passes through an ion trap that captures ions from the plasma, such that mainly radicals pass through as a radical stream and reach the surface of the substrate. In some embodiments, the ion trap is a mesh plate. In some embodiments, the radical stream contains nitrogen radicals, hydrogen radicals, oxygen radicals, or a combination thereof. Generally, the RF power used to generate the plasma is maintained between 50 - 1000 W.

[0108] In one embodiment, steps 204, 206, 208, and 220 can be repeated until the target film thickness 212 is reached. The number of repetition cycles (n) is not particularly limited and can be between 1 and about 5000. In some embodiments, the number of repetition cycles (n) is typically between 1 and about 2000, between 1 and about 1000, between 1 and about 500, between 1 and about 200, between 1 and about 100, or more typically between about 10 and about 1000, more typically between about 10 and about 500, more typically between about 10 and about 200, more typically between about 10 and about 100, or even more typically between about 50 and about 1000, even more typically between about 50 and about 500, or even more typically between about 50 and about 200. The number of repetitions (n) of the deposition cycle depends on the growth rate of the deposited material and the desired thickness of the film. In one embodiment, after a certain number of deposition steps 104, the substrate is exposed to a radical stream 106. For example, step 106 can be performed after 10 deposition cycles, or after 20 deposition cycles, or after 30 deposition cycles. The method and each process step will be described in more detail below.

[0109] Finally, during step 214, at least one gap in the substrate is filled with a material including silicon and nitrogen.

[0110] Now turning to Figure 3 , a reactor system 300 according to an exemplary embodiment of the present disclosure is shown. The reactor system 300 can be used to perform one or more steps or sub-steps as described herein and / or form one or more device structures or portions thereof as described herein.

[0111] The reactor system 300 includes a pair of conductive flat plate electrodes 314, 318 that are parallel and face each other within the interior 301 (reaction zone) of the reaction chamber 302. By applying plasma power, such as from plasma power source 308, to one electrode (e.g., electrode 318) and electrically grounding the other electrode (e.g., electrode 314), plasma can be excited within the reaction chamber 302. A temperature regulator 303 can be provided in the lower platform 314 (lower electrode), and the temperature of the substrate 322 placed thereon can be maintained at a desired temperature, such as the above-mentioned temperature. Electrode 318 can be used as a gas distribution device, such as a shower plate or a shower head. One or more gas lines (e.g., reactant gas line 304 and precursor gas line 306 that are respectively connected to a reactant source and a precursor source) can be used to introduce precursor gases, reactant gases, carrier gases, or inert gases (if any) into the reaction chamber 302. For example, an inert gas and a reactant (e.g., as described above) can be introduced into the reaction chamber 302 using line 304 and / or a precursor and a carrier gas (e.g., the inert gas as described above) can be introduced into the reaction chamber 302 using line 306. Although shown as having two inlet gas lines 304, 306, the reactor system 300 can include any suitable number of gas lines.

[0112] In the reaction chamber 302, a circular duct 320 having an exhaust gas line 321 can be provided, and the gas in the interior 301 of the reaction chamber 302 can be exhausted to an exhaust source 310 through this duct. Additionally, a transfer chamber 323 can be provided with a seal gas line 329 to introduce seal gas into the interior 301 of the reaction chamber 302 via the interior (transfer zone) of the transfer chamber 323, where a separation plate 325 for separating the reaction zone 301 and the transfer chamber 323 can be provided (gate valves are omitted from this figure, and the substrate is transferred into or out of the transfer chamber 323 through these gate valves). The transfer chamber 323 can also be provided with an exhaust gas line 327 connected to the exhaust source 310. In some embodiments, a flow-through system (FPS) can be used to achieve a continuous flow of carrier gas into the reaction chamber 302.

[0113] The reactor system 300 can include one or more controllers 312 that are programmed or otherwise configured to perform one or more method steps as described herein. As will be understood by those skilled in the art, the controller 312 is coupled to various power supplies, heating systems, pumps, robots, and gas flow controllers or valves of the reactor. By way of example, the controller 312 can be configured to control the flow of precursors, reactants, and inert gases into at least one of the one or more reaction chambers to form a layer on the surface of a substrate. The controller 312 can be further configured to provide power to form a plasma—e.g., within the reaction chamber 302. The controller 312 can be similarly configured to perform additional or alternative steps as described herein. As an example, the controller 312 can be configured to perform steps of processing deposited materials, etching, and / or curing.

[0114] The controller 312 can include electronic circuitry and software to selectively operate valves, manifolds, heaters, pumps, and other components included in the system 300. Such circuitry and components operate to introduce precursors, reactants, and purge gases from their respective sources. The controller 312 can control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber, the pressure within the reaction chamber, and various other operations to provide proper operation of the system 300.

[0115] The controller 312 can include control software to control valves electrically or pneumatically to control the flow of precursors, reactants, and / or purge gases into and out of the reaction chamber 302. The controller 312 can include modules that perform certain tasks, such as software or hardware components, e.g., FPGA or ASIC. The modules can be advantageously configured to reside on an addressable storage medium of the control system and configured to perform one or more processes.

[0116] In some embodiments, a dual-chamber reactor (two sections or compartments for processing substrates disposed close to each other) can be used, where reactant gases and inert gases can be supplied through a common line, while precursor gases are supplied through non-common lines.

[0117] During operation of the system 300, a substrate (e.g., a semiconductor wafer) is transferred from, for example, a substrate edge region 323 to the reaction zone 301. Once the substrate(s) is transferred to the reaction zone 301, one or more gases (such as precursors, reactants, carrier gases, and / or purge gases) are introduced into the reaction chamber 302.

[0118] Figure 4An example of an embodiment of a radical processing chamber is shown, where a remote plasma unit (RPU) 408 upstream of the reaction chamber 400 is used to form a plasma. In some embodiments, the RPU includes an inductively coupled plasma. Optionally, a second plasma source may be provided. For example, the second plasma source 415 can be electrically connected to the showerhead 410, allowing the showerhead to be biased relative to the pedestal 412 to form a second plasma discharge therebetween. A carrier gas is supplied from a first carrier gas source 402 through a gas manifold 401 and passes through the RPU 408 and enters the reaction chamber 400 through the showerhead 410, which is positioned directly above the pedestal 412, and a wafer 411 (i.e., a planar substrate) is placed on the pedestal 412. The reactive gas can be vaporized and entrained in the carrier gas or pulsed into the carrier gas. The apparatus is also configured to allow other gases to flow through the RPU 408 from an optional third source 404.

[0119] For example, in some cases, it may be beneficial to introduce a cleaning gas (e.g., NF3 diluted in an inert gas) periodically or even between each reaction cycle to remove any deposits from decomposed precursor chemicals in one or more of the gas lines, the gas manifold 401, the RPU 408, and the showerhead 410. Additional gases (e.g., carrier gas, diluent gas, processing gas, feed gas, and / or purge gas) from a second source 406 can flow through the showerhead 410 from a second gas manifold 405 or into the reaction chamber 400 from other ports (not shown). Unreacted gases and gaseous reaction by-products leave the bottom of the reaction chamber through an exhaust line 413. The reaction chamber can optionally be equipped with a purge line and / or a pump line connected to a vacuum pump such that the chamber can be purged between various reaction cycles (not shown). The apparatus also includes a controller 414, which is operably connected to a first gas valve 416, a second gas valve 418, and a third gas valve 418 on the first gas manifold 401, a first gas valve 419 and a second gas valve 420 on the second gas manifold 405, an RF power supply for the RPU 409, a second optional RF power supply 415, and other components (not shown). Optionally, the apparatus also includes an ion trap 421, which can be positioned between the showerhead 410 and the wafer 411 to confine the plasma region to the upper portion of the chamber above the ion trap. For example, an electrically grounded grid plate can be used as the ion trap. In some embodiments, the grid plate is a metal plate including hundreds of holes in a showerhead-like pattern, which allows radical species to pass through to reach the wafer 411 while trapping ions. For example, the grid plate can include between about 1000 and about 5000 holes, and each hole has a diameter between about 0.5 mm and about 2 mm. The addition of the ion trap advantageously reduces or even eliminates the interaction of electrons and ions with the wafer surface by confining the plasma to the plasma region in the upper portion of the reaction chamber 400.

[0120] The controller 414 is configured and programmed to independently control (e.g., turn on and off, etc.) the supply of various gases (e.g., carrier gas, reactive gas, and any diluent, process gas, feed gas, and / or purge gas, etc.), the plasma source, and an optional second plasma source to treat the film on the surface of the wafer 412 with a radical flow as needed. For example, in some embodiments, the controller 414 opens the valve 419 to allow the reactive gas to flow from the second source 406 into the reaction chamber 400 and turns on the RF power supply 409 in the RPU. After a set period of time, the controller 414 turns off the RF power supply 409. After a set period of time, the controller 414 closes the valve 419 leading to the reactive gas 406. The controller 414 is programmed to repeat various process steps to treat the film on the surface of the wafer 411 with a radical flow. The controller 414 can be programmed to perform other processing steps between these various steps.

[0121] The illustrations presented herein are not meant to be actual views of any particular material, structure, or device, but are merely idealized representations for describing embodiments of the present disclosure.

[0122] The specific embodiments shown and described are illustrative of the invention and its best mode and are not intended to limit the scope of the aspects and embodiments in any way. Indeed, for the sake of brevity, conventional manufacturing, connection, preparation, and other functional aspects of the system may not be described in detail. Additionally, the connecting lines shown in the figures are intended to represent exemplary functional relationships and / or physical couplings 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.

[0123] 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 regarded as limiting in any way since many variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Accordingly, the various acts shown may be performed in the order shown, in other orders, or in some cases may be omitted.

[0124] The subject matter of the present disclosure includes all novel and non - obvious combinations and sub - combinations of the various processes, systems, and configurations, as well as other features, functions, acts, and / or properties disclosed herein, and any and all equivalents thereof.

Claims

1. A method of filling gaps with a material containing silicon and nitrogen, the method comprising the steps of: Providing a substrate into a reaction chamber, wherein the substrate includes at least one gap; Depositing a material containing silicon and nitrogen; and Treating the deposited material using radical treatment.

2. The method according to claim 1, wherein The depositing step is carried out in a deposition reaction chamber, and the radical treatment step is carried out in a radical treatment chamber; and the deposition reaction chamber and the radical treatment chamber are operatively coupled to allow the substrate to be transferred between them without any air interruption.

3. The method according to claim 1 or 2, wherein, The method further includes a thermal curing step between the depositing step and the treating step.

4. The method according to claim 3, wherein, The thermal curing step is carried out in a thermal curing chamber, and the thermal curing chamber is operatively coupled to the deposition reaction chamber and the radical treatment chamber to allow the substrate to be transferred between them without any air interruption.

5. The method according to any one of the preceding claims, wherein, The method further includes the step of exposing the deposited material to vacuum ultraviolet radiation.

6. The method according to claim 5, wherein, The step of exposing the deposited material to vacuum ultraviolet radiation occurs in a vacuum ultraviolet radiation chamber, and the vacuum ultraviolet radiation chamber is operatively coupled to the deposition reaction chamber, the radical treatment chamber, and the thermal curing chamber to allow the substrate to be transferred between them without any air interruption.

7. The method according to any one of the preceding claims, wherein, The deposited material further includes carbon.

8. The method according to any one of the preceding claims, wherein, The depositing step includes performing at least one deposition cycle, and one deposition cycle includes: Providing a silicon precursor in a gas phase into the reaction chamber; and Providing deposition plasma power to form activated species from reactants.

9. The method according to claim 8, wherein, The reactants include nitrogen gas.

10. The method according to claim 8, wherein, The reactants include nitrogen gas and argon gas.

11. The method according to any one of the preceding claims, wherein, The silicon precursor includes aminosilane or silazane.

12. The method according to any one of the preceding claims, wherein, The silicon precursor is selected from bis(diethylamino)silane, diisopropylaminosilane, N-(diethylaminosilyl)-N-ethylethylamine, N,N'-dimethylsilylsilanediamine, hexamethyldisilazane, hexamethyltrisilazane, tetramethyldivinyldisilazane, tetramethyldisilazane, and tetraisocyanatosilane.

13. The method according to any one of the preceding claims, wherein, The thermal curing step includes treating the deposited material at a temperature between 400 °C and 600 °C.

14. The method according to claim 5, wherein, The wavelength of the vacuum ultraviolet radiation is 100 - 450 nm.

15. The method according to claim 5, wherein The wavelength of the vacuum ultraviolet radiation is 172 nm.

16. The method according to any one of the preceding claims, wherein, The radical treatment includes: Generating a remote plasma; Obtaining a radical stream from the remote plasma; and Exposing the substrate to the radical stream.

17. The method according to claim 16, wherein The radical stream is obtained from the remote plasma using an ion trap.

18. The method according to claim 17, wherein, The ion trap is disposed in the reaction chamber between the remote plasma discharge and the substrate.

19. The method according to claim 16 or 17, wherein The ion trap is an electrically grounded grid plate.

20. The method according to claim 16, wherein The remote plasma discharge is generated by gas phase ionization of a gas having a radio frequency (RF) power of 3000 W or less.

21. The method according to claim 16, wherein The remote plasma discharge is generated by gas phase ionization of a gas having a radio frequency (RF) power of 600 W or less.

22. The method according to claim 16, wherein The radical stream contains hydrogen radicals.

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