Substrate processing apparatus and method

Abstract

A substrate processing method and apparatus for producing a sacrificial masking layer are disclosed. The layer is produced by selectively growing the sacrificial masking layer by providing a first precursor in a reaction chamber that reacts with one of the radiation-modified and unmodified layer portions on the substrate but not with the other of the radiation-modified and unmodified layer portions.

Description

Technical Field

[0001] This disclosure generally relates to a substrate processing apparatus and a method for producing a sacrificial masking layer.

[0002] Substrate processing apparatus for producing a sacrificial masking layer on a substrate may include photolithography input / output ports for transferring the substrate between the substrate processing apparatus and the photolithography projection apparatus.

[0003] Substrate fabrication methods for producing sacrificial masking layers may include:

[0004] A substrate with a radiation-modified layer is provided to the photolithography projection device for patterning, and

[0005] The radiation-modified layer of the substrate is patterned by exposing the radiation-modified layer to radiation using a photolithography projection device. Background Technology

[0006] Different process steps can be performed on the substrate using substrate processing equipment (such as a track or coating machine) before and / or after patterning in the resist layer on the substrate. For example, if contaminants are present on the substrate, they can be removed by chemical treatment. The substrate can be heated to a temperature sufficient to expel any moisture that may be present on the substrate. Adhesion promoters can be applied to promote the adhesion of the resist to the substrate.

[0007] In a resist deposition apparatus of a substrate processing device, a substrate can be coated with a resist layer, for example, by spin-coating a resist. A viscous liquid solution of resist can be dispensed onto the substrate, and the substrate can be rotated to produce a uniform thin layer. The resist-coated wafer can then be baked to evaporate the resist solvent.

[0008] A substrate with a resist layer can be transferred from a substrate processing apparatus to a photolithography projection apparatus. In the photolithography projection apparatus, the substrate with the resist layer can be exposed to a patterning radiation beam of (extreme) ultraviolet radiation. Exposure to radiation causes a chemical change in the resist layer, thereby patterning the layer.

[0009] For EUV lithography, the resist layer can be very thin. Such a thin layer may not be very etch-resistant. Summary of the Invention

[0010] This overview is provided to introduce a set of concepts in a simplified form. These concepts are described in more detail below in the detailed description of exemplary embodiments of this disclosure. This overview 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.

[0011] In some embodiments, a substrate processing apparatus may be provided for generating a sacrificial masking layer on a substrate. The substrate processing apparatus may include a lithography input / output port for transferring the substrate between the substrate processing apparatus and a lithography projection apparatus. The substrate processing apparatus may provide a selective deposition apparatus to provide a first precursor in a reaction chamber that is selectively reacted with one of radiation-modified and unmodified layer portions but not with the other of the radiation-modified and unmodified layer portions to generate a sacrificial masking layer. The apparatus may include a substrate loader for transferring the substrate between the lithography input / output port and the selective deposition apparatus. The apparatus may include a control system operatively connected to the substrate loader and the selective deposition apparatus. The control system may provide a memory that, when executed on the control system, controls: controlling the substrate loader to pick up the substrate from the lithography input / output port and move it to the selective deposition apparatus; and controlling the selective deposition apparatus to provide a first precursor in a reaction chamber that is selectively reacted with one of the radiation-modified and unmodified layer portions but not with the other of the radiation-modified and unmodified layer portions to generate a sacrificial masking layer.

[0012] In some embodiments, a substrate processing method for producing a sacrificial masking layer is disclosed. The substrate processing method may include providing a substrate having a radiation-modified layer to a photolithography projection apparatus for patterning. The substrate processing method may further include patterning the radiation-modified layer of the substrate by exposing the radiation-modified layer to radiation using the photolithography projection apparatus. The substrate may be moved from the photolithography projection apparatus to a reaction chamber of a selective deposition apparatus. A first precursor may be provided in the reaction chamber, selected to react with one of the modified and unmodified layer portions but not with the other of the modified and unmodified layer portions, to produce the sacrificial masking layer.

[0013] For the purpose of summarizing the invention and its advantages over the prior art, certain objectives and advantages of the invention have been described in the foregoing. It should be understood, of course, that not all such objectives or advantages may be achieved according to any particular embodiment of the invention. Therefore, by way of example, those skilled in the art will recognize that the invention may be embodied or practiced in a manner that achieves or optimizes one or more advantages taught or stated herein, without necessarily achieving other objectives or advantages that may be taught or stated herein.

[0014] All these embodiments are intended to be included within the scope of the disclosed invention. These and other embodiments will be apparent to those skilled in the art from the following detailed description of certain embodiments taken in conjunction with the accompanying drawings, and the invention is not limited to any particular embodiment disclosed. Attached Figure Description

[0015] Although this specification concludes with claims that specifically point out and expressly claim protection to the contents regarded as embodiments of the invention, the advantages of embodiments of the present disclosure can be more readily determined by reading in conjunction with the accompanying drawings, which illustrate certain examples of embodiments of the present disclosure:

[0016] Figure 1 This illustration shows a substrate processing method according to at least one embodiment of the present disclosure.

[0017] Figure 2 It indicates that it is applicable to Figure 1 Substrate processing apparatus for substrate processing methods.

[0018] Figure 3 It indicates the use of Figure 2 Selective deposition equipment for substrate processing apparatus.

[0019] Figure 4 and 5 This illustrates a resist-free patterning method according to an embodiment of the present invention. Throughout... Figure 4 and 5 In the middle, follow the following numbering: 410 – Radiation-modified layer; 411 – Radiation-modified layer portion; 412 – Unmodified layer portion; 420 – Lower layer; 430 – Substrate; 440 – Sacrificial masking layer; 450 – Recess. Detailed Implementation

[0020] Although certain embodiments and examples are disclosed below, those skilled in the art will understand that the invention extends beyond the specific embodiments and / or uses disclosed herein, as well as obvious modifications and equivalents thereof. Therefore, it is intended that the scope of the invention be limited not to the specific disclosed embodiments described below. Furthermore, 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.

[0021] As used herein, the term "substrate" can refer to any one or more underlying materials on which devices, circuits, or films can be formed. Additionally, the term "modifiable layer" can refer to any material to which other species, such as atoms, molecules, or ions, can be introduced. The term "semiconductor device structure" can refer to any portion of a fabricated or partially fabricated semiconductor structure that is, includes, or defines at least a portion of the active or passive components of a semiconductor device to be formed on or in a semiconductor substrate. For example, a semiconductor device structure may include active and passive components of an integrated circuit, such as transistors, memory elements, transducers, capacitors, resistors, conductive lines, conductive vias, and conductive pads.

[0022] As used herein, the term "precursor" can refer to a compound that participates in a chemical reaction that produces another compound, and in particular to a compound that constitutes the membrane matrix or main framework of the membrane; the term "reactant" is used interchangeably with the term "precursor." Depending on the context, a precursor can include materials that are gases at ambient temperature and pressure (NTP), vaporized solids and / or vaporized liquids, and can consist of a single gas or a mixture of gases.

[0023] The term "atomic layer deposition" can refer to a vapor phase deposition process in which deposition cycles, typically multiple consecutive deposition cycles, are performed in a process chamber. When performed using alternating pulses of precursor / reactive gases and purge gases (e.g., inert carrier gases), as used herein, the term "atomic layer deposition" is also intended to include processes specified by related terms such as chemical vapor deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, or organometallic MBE and chemical beam epitaxy.

[0024] Typically, for ALD processes, during each cycle, a precursor is introduced into the reaction chamber and chemisorbed onto the deposition surface (e.g., a substrate surface, which may contain previously deposited material from previous ALD cycles or other materials), forming a nearly monolayer or submonolayer material that is not readily reactive with additional precursors (i.e., a self-limiting reaction). Subsequently, reactants (e.g., another precursor or reactive gas) may be introduced into the process chamber to convert the chemisorbed precursor into the desired material on the deposition surface. The reactants may be able to further react with the precursor. During one or more cycles, such as during each step of each cycle, a purging step may be employed to remove any excess precursor from the process chamber and / or any excess reactants and / or reaction byproducts from the reaction chamber.

[0025] Numerous example materials may be given throughout the embodiments of this disclosure. It should be noted that the chemical formulas given for each example material should not be construed as limiting, and the non-limiting example materials given should not be limited to the given example stoichiometry.

[0026] One object of this disclosure is to provide patterning apparatus and methods that will avoid adhesion problems that may occur between the photoresist and the underlying layer.

[0027] Another object of this disclosure is to provide patterning apparatus and methods for preventing photoacid segregation to the resist / air interface.

[0028] Another object of this disclosure is to provide patterning apparatus and methods that allow photolithography processes to be substantially free of dross defects and / or resist line breaks.

[0029] Another object of this disclosure is to provide patterning apparatus and methods that will allow the lithography process to be substantially free of pattern collapse.

[0030] Another object of this disclosure is to provide patterning apparatus and methods that will allow the deposition of photolithographic layers with high etch budgets.

[0031] Figure 1 An exemplary substrate fabrication method according to at least one embodiment is illustrated. Embodiments may include a substrate fabrication method for producing a sacrificial masking layer.

[0032] The substrate processing method 30 may include: in step 32, providing a substrate to, for example, a modifiable layer deposition apparatus; in step 34, depositing a radiation-modifiable layer on the substrate in the modifiable layer deposition apparatus; and in step 36, moving the substrate with the radiation-modifiable layer to a photolithography projection apparatus for local modification, such as patterning. The substrate with the modifiable layer may also be obtained from other locations.

[0033] In fact, the modifiable layer can also be the top surface of the substrate or a layer provided as the top surface. The high-energy radiation of EUV can change the properties of the top surface, which can produce selectivity in selective deposition processes to produce an etch mask.

[0034] In some embodiments, the modifiable layer comprises carbon and may contain chemical bonds selected from C, CN, and CO bonds. Such bonds can be appropriately broken by means of EUV radiation, thereby locally altering the properties of the modifiable layer in the exposed region. Such localized modification can then be used to achieve region-selective deposition.

[0035] In some embodiments, the radiation-modified layer comprises one or more elements selected from Sn, Sb, Hf, In, and Te. Alternatively, elements selected from Sn, Sb, Hf, In, and Te may be provided in the underlying layer on which the radiation-modified layer is deposited. Therefore, in some embodiments, the process for depositing the radiation-modified layer involves depositing the radiation-modified layer on an underlying layer comprising elements selected from Sn, Sb, Hf, In, and Te. The underlying layer may comprise, for example, SiOC and / or SiOCN, and may be deposited using well-known methods, such as PECVD or PEALD. Without being bound by any theory or particular operating mode, these elements are believed to improve the sensitivity of the modifiable layer to EUV radiation through their relatively high trapping cross-section for EUV photons.

[0036] In a photolithography projection apparatus, the radiation-modified layer of the substrate can be patterned in step 38 by exposing the radiation-modified layer to the radiation source using the photolithography projection apparatus; and in step 40, the substrate is moved from the photolithography projection apparatus to the reaction chamber of a selective deposition apparatus. In a selective deposition apparatus, a first precursor can be provided in the reaction chamber to react with one of the modified and unmodified layer portions but not with the other of the modified and unmodified layer portions to produce a sacrificial masking layer in step 42.

[0037] Because the first precursor reacts only with one of the modified and unmodified layer portions and not with the other, a sacrificial masking layer whose etch resistance is independent of the thickness of the radiation-modified layer can be produced. The radiation-modified layer provided in step 34 may have a single-layer thickness. The radiation-modified layer may have more than a single-layer thickness. The radiation-modified layer may have a thickness between 0.1 and 50 nm, or between 0.5 and 40 nm, more preferably between 5 and 20 nm. In some embodiments, the radiation-modified layer may have a thickness of at least 0.1 nm to at most 0.5 nm, or at least 0.5 nm to at most 1.0 nm, or at least 1.0 nm to at most 2.0 nm, or at least 2.0 nm to at most 5.0 nm, or at least 5.0 nm to at most 10.0 nm, or at least 10.0 nm to at most 20.0 nm, or at least 20.0 nm to at most 50.0 nm.

[0038] According to this disclosure, it may be unnecessary to remove some of the radiation-modified layer with a special developer solution immediately after exposure to radiation patterning using a photolithography projection apparatus. At very small feature sizes, there is a risk of pattern collapse after removing a portion of the radiation-modified layer. The risk of pattern collapse can be increased with thicker radiation-modified layers. By not removing a portion of the radiation-modified layer with a developer solution, the radiation-modified layer can be better stabilized.

[0039] The first precursor may be selected to react with one of the modified and unmodified layer portions but not with the other. Etching resistance can be altered by reacting the first precursor with one of the modified and unmodified layer portions, thereby creating a sacrificial masking layer. The substrate can be etched using the sacrificial masking layer, thereby removing one of the modified and unmodified layer portions. After etching, the sacrificial masking layer can be completely removed if it is no longer needed.

[0040] Therefore, in some embodiments of this disclosure, a radiation-modified layer can be used to form a plurality of recesses in a substrate. In such embodiments, a sacrificial masking layer can be suitable for deposition on either the radiation-modified layer portion or the unmodified layer portion. The sacrificial masking layer can be deposited, for example, via plasma-enhanced atomic layer deposition (ALD), thermal ALD, radical-enhanced ALD (REALD), plasma-enhanced chemical vapor deposition (CVD), or thermal CVD deposition.

[0041] In some embodiments, the sacrificial masking layer is deposited via a selective ALD process, which employs a contrast ratio of OH groups to CH groups. x A more reactive precursor is one containing a group (where x is an integer from 1 to 3). Advantageously, the precursor used in such embodiments is more reactive to CH. x The group (where x is an integer from 1 to 3) is substantially non-reactive, but highly reactive to the OH group. Examples of processes employing precursors that are more reactive to the OH group than to the CH3 group include ALD of TiN or TiO2 using TiCl4 and NH3 or H2O, TDMAT (tetra(dimethylamino)titanium) and H2O, and / or TTIP (tetraisopropoxide titanium) and H2O. Another example of a process employing a precursor that is more reactive to the OH group includes ALD of Ru via EBECHRu (ethyl-phenylethyl-1,4-cyclohexadiene ruthenium). Without being bound by any particular theory or mode of operation, these processes are believed to exhibit nucleation retardation on CH3-terminated surfaces relative to OH-terminated surfaces, which can be utilized to provide selective growth on OH-terminated surfaces relative to CH3-terminated surfaces.

[0042] In some embodiments, the sacrificial masking layer is deposited via a selective ALD process, which employs a contrast ratio of OH groups to CH groups. x The precursors with less reactive groups (where x is an integer from 1 to 3) are preferred. Advantageously, the precursors used in such embodiments are less reactive than CH4. x The radical (where x is an integer from 1 to 3) is highly reactive, while it is less reactive or unreactive to OH groups. Such a process can be used in CH4 x A sacrificial masking layer is selectively deposited on the end-capping surface relative to the OH end-capping surface. For example, the precursor may contain ruthenium tetroxide and H2 may be used as a reagent. Therefore, the ruthenium-containing sacrificial masking layer can be deposited on CH4, for example, by thermal ALD or plasma-enhanced ALD. x Selective deposition on the end cap surface relative to the OH end cap surface.

[0043] After the sacrificial masking layer has been deposited, an etching step can be performed on the substrate. Suitable etching steps are well known in the art. If necessary, the sacrificial masking layer can be removed using well-known techniques after the etching step.

[0044] Optionally, the sacrificial masking layer deposition step and the etching step can be performed in the same reaction chamber. Optionally, any sacrificial masking layer removal step can also be performed in the same reaction chamber.

[0045] Non-limiting examples of the substrate processing apparatus disclosed herein may be found in Figure 2 The diagram illustrates an exemplary substrate processing apparatus 1 according to embodiments of the present disclosure. It should be noted that... Figure 2 The substrate processing apparatus 1 shown in the diagram is a simplified schematic version of an exemplary substrate processing apparatus and does not include every component that may be used in the manufacture of the substrate processing apparatus of this disclosure, such as every valve, gas line, heating element, and reactor component.

[0046] An exemplary substrate processing apparatus 1 may include a wafer cassette loading / unloading section 2 on which a wafer cassette 3 having a plurality of substrates 15 may be placed. The wafer cassette loading / unloading section 2 may act as a wafer fab input / output port to transfer the substrates 15 within the wafer cassette 3 between the substrate processing apparatus and the remainder of the wafer fab. The substrate processing apparatus 1 may be adapted to... Figure 1 Substrate processing methods.

[0047] The substrate processing apparatus may have a photolithography input / output port 5. The substrate may be transferred to the photolithography projection apparatus via the photolithography input / output port 5.

[0048] The substrate processing apparatus may include a processing section 4. The processing section 4 may be provided with a modifiable layer deposition apparatus 7 for depositing a radiation-modifiable layer on the substrate.

[0049] The modifiable layer deposition apparatus 7 may include a radiation-modified coating apparatus for coating a radiation-modified material (e.g., a photoresist) onto a substrate. The modifiable layer deposition apparatus 7 may include a rotatable substrate stage 17 for rotating the substrate and a liquid dispenser for supplying liquid to the surface of the substrate. The radiation-modified material (e.g., a photoresist) in liquid form may be supplied to the substrate while the substrate can rotate at 10 to 100 revolutions per second for 20 to 60 seconds.

[0050] A substrate loader 6 may be provided in the processing section 4 to transfer the substrate between the wafer cassette 3, the modifiable layer deposition equipment 7, and the lithography input / output port 5 at the wafer cassette loading and unloading section 2. For this purpose, the substrate loader 6 may have a substrate holder that can move in both horizontal and vertical directions.

[0051] A selective deposition apparatus 11 may be provided in the processing unit 4, the selective deposition apparatus having a reaction chamber 12 and a substrate stage 13 for holding a substrate in the reaction chamber 12. A first precursor may be provided in the reaction chamber to react with one of the radiation-modified and unmodified layer portions but not with the other of the radiation-modified and unmodified layer portions to produce a masking layer. The selective deposition apparatus may include a precursor dispensing and removal system 14, which includes one or more reaction chamber valves to provide a gaseous first precursor to the reaction chamber 12 and to remove the gaseous first precursor from the reaction chamber. A substrate loader 6 may be configured and arranged to move a substrate to and from the selective deposition apparatus 11.

[0052] The substrate processing apparatus 1 may provide a control system 8, which is operatively connected to the substrate loading / unloading device 6, the radiation-modified layer deposition apparatus 7, and the selective deposition apparatus 11, and is provided with a memory M containing programs. When the program in the memory M is executed on the control system 8, it can:

[0053] The control substrate loading and unloading device 6 picks up the substrate 15 from the wafer cassette 3 at the wafer cassette loading and unloading section 2, moves the substrate to the modifiable layer deposition equipment 7 and places it on the rotatable substrate stage 17.

[0054] The radiation-modified layer deposition apparatus 7 is controlled to deposit a radiation-modified layer on a substrate on a rotatable substrate stage 17; and,

[0055] The control substrate loading / unloading device 6 picks up the substrate from the rotatable substrate stage 17 and moves the substrate to the photolithography projection apparatus via the photolithography input / output port 5, for example via the first and second substrate stages 16 at the photolithography input / output port 5. After the photolithography projection apparatus locally modifies the radiation-modified layer with exposed radiation, the substrate can be transferred back to the substrate processing apparatus via the photolithography input / output port 5.

[0056] The program in the memory M of the executable controller 8 is:

[0057] The substrate loading / unloading device 6 picks up the substrate via the photolithography input / output 5 and moves the substrate to the selective deposition apparatus 11; and,

[0058] The selective deposition apparatus 11 provides a first precursor, selected to react with one of the radiation-modified and unmodified layer portions but not with the other, within a reaction chamber having a precursor dispensing and removal system 14, to produce a sacrificial masking layer; and,

[0059] The substrate loading / unloading device 6 picks up the substrate from the selective deposition equipment 11 and moves it to the wafer fab input / output port 2.

[0060] A heating station 9 and a cooling station 10 can be provided in the processing section 4 to bake and cool the substrate, respectively. The heating station 9 and the cooling station 10 can also be supplied with the substrate by the substrate loading and unloading device 6. Heating and / or cooling may be required before the substrate is transferred to the photolithography projection apparatus.

[0061] When, for example, a substrate with a radiation-modifiable layer is obtained from elsewhere, the modifiable layer deposition apparatus 7 can be omitted. In such a case, the substrate handler may not need to move the substrate to the modifiable layer deposition apparatus and move the substrate from the modifiable layer deposition apparatus to the photolithography projection apparatus via the photolithography input / output port.

[0062] Figure 3 It indicates the use of Figure 2 A non-limiting exemplary selective deposition apparatus 11 is described in the substrate processing apparatus 1. The selective deposition apparatus 11 may include a reaction chamber 12 configured and arranged to hold at least one substrate 15 on which a radiation-modified layer 106 is provided.

[0063] The reaction chamber 12, capable of selective deposition of a (first) precursor, may include reaction chambers configured for atomic layer deposition (ALD) processes, or plasma-enhanced atomic layer deposition (PEALD) or radical-enhanced atomic layer deposition (REALD), and reaction chambers configured for chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), or metal-organic CVD (MOCVD) processes. The reaction chamber 12 may also be capable of in-situ directional plasma etching or connected to a reaction chamber 12b designed for plasma etching capabilities. According to some embodiments, a spray-head reaction chamber may be used. According to some embodiments, cross-flow, batch, small-batch, immersion, or spatial ALD reaction chambers may be used.

[0064] In some embodiments of this disclosure, a batch reaction chamber may be used. In some embodiments, a vertical batch reaction chamber may be used. In other embodiments, the batch reaction chamber includes a small-batch reactor configured to accommodate 10 or fewer wafers, 8 or fewer wafers, 6 or fewer wafers, 4 or fewer wafers, or 2 or fewer wafers.

[0065] A substrate holder 13 having at least one substrate 15 may be disposed within the reaction chamber 12, wherein a radiation-modified layer 106 is disposed on the upper surface of the substrate 15. In some embodiments of this disclosure, the substrate 15 may include a planar substrate or a patterned substrate.

[0066] In some embodiments, the formation of the radiation-modified layer includes depositing a lower layer, such as an amorphous carbon (sp3 / sp2 carbon) lower layer, on a substrate. The amorphous carbon lower layer can be deposited, for example, by means of a hydrocarbon-containing precursor and a plasma such as a rare gas plasma, such as helium plasma or argon plasma. The radiation-modified layer can be formed on the surface of the lower layer by means of a further plasma treatment. In some embodiments, the radiation-modified layer includes surface functional groups, such as NH2, Cl, F, and CH3 functional groups, on the amorphous carbon lower layer. In an exemplary embodiment, such groups can be formed on the surface of the lower layer by subjecting the amorphous carbon lower layer to plasma treatment, wherein a plasma containing F, Cl, N, and / or H is used. The NH2, Cl, F, and / or CH3 functional groups thus formed are impaired upon exposure to extreme ultraviolet (EUV) radiation due to the breaking of C-NH2, C-Cl, CF, and / or C-CH3 bonds and can subsequently be replaced by C-OH groups when the wafer is exposed to oxygen. Oxygen can be provided, for example, by exposure to the reaction chamber or by exposing the substrate to the atmosphere.

[0067] (i) In some embodiments, the formation of the radiation-modified layer includes the deposition of a self-assembled monolayer (SAM). In this case, EUV radiation can be used to remove one or more functional groups from the SAM, thereby modifying the radiation-modified layer. Exemplary functional groups that can be removed by means of EUV radiation include NH2, Cl, F, I, Br, and CH3. Removing one or more of these functional groups can significantly alter the surface properties of the exposed areas of the SAM-coated substrate. In some embodiments, the SAM can be deposited by means of CVD deposition in an immersion mode, i.e., by exposing the substrate to SAM vapor until the adsorption of SAM on the substrate reaches saturation. Alternatively, the SAM can be deposited by means of multiple SAM precursor pulses. This can improve the densification of the SAM layer. The pulses can last for, for example, 0.1 to 1.0 seconds, or 1.0 to 2.0 seconds, or 2.0 to 5.0 seconds, or 5.0 to 10.0 seconds, or 10.0 to 20.0 seconds.

[0068] In some embodiments, the radiation-modified layer comprises a polymer film. Such a polymer film can be deposited, for example, by means of molecular layer deposition. Suitable films include polyimide, polyamide, and polyurea films. Exemplary polymer films can be deposited by means of the method disclosed in U.S. Patent US10343186B2, the entire contents of which are incorporated herein by reference.

[0069] The substrate 15 may comprise one or more materials, including but not limited to silicon (Si), germanium (Ge), germanium-tin (GeSn), silicon-germanium (SiGe), silicon-germanium-tin (SiGeSn), silicon carbide (SiC), or III-V group semiconductor materials such as gallium arsenide (GaAs), gallium phosphide (GaP), or gallium nitride (GaN). In some embodiments of this disclosure, the substrate 15 may comprise a engineered substrate, wherein a surface semiconductor layer is disposed above a body support, and an intermediate buried oxide (BOX) is disposed therebetween.

[0070] Patterned substrates may include semiconductor device structures formed in or on the surface of the substrate. For example, a patterned substrate may include partially fabricated semiconductor device structures, such as transistors and / or memory elements. In some embodiments, the substrate may contain a single-crystal surface and / or one or more subsurfaces, which may include non-single-crystal surfaces, such as polycrystalline surfaces and / or amorphous surfaces. Single-crystal surfaces may contain one or more of, for example, silicon (Si), silicon-germanium (SiGe), germanium-tin (GeSn), or germanium (Ge). Polycrystalline or amorphous surfaces may contain dielectric materials, such as oxides, oxynitrides, or nitrides, such as silicon oxide and silicon nitride.

[0071] In some embodiments of this disclosure, substrate 15 has a radiation-modified layer 106 disposed thereon, i.e., disposed on the upper surface of substrate 15. Radiation-modified layer 106 may contain any material that, upon exposure to radiation, can selectively react with a (first) precursor to selectively grow a masking layer on radiation-modified layer 106.

[0072] In some embodiments of this disclosure, the radiation-modified layer 106 may comprise at least one of polymeric resists such as photoresists, extreme ultraviolet (EUV) resists, immersion photoresists, chemically amplified resists (CAR), or electron beam resists (e.g., poly(methyl methacrylate) (PMMA)). The radiation-modified layer 106 may also be a metal, oxide, self-assembled monolayer (SAM), or any other material. Alternatively or additionally, the radiation-modified layer 106 may comprise C, N, H, and / or O. Optionally, the radiation-modified layer comprises CF bonds, C-Cl bonds, and / or C-NH2 bonds. These bonds can be broken by means of EUV photon irradiation, resulting in locally altered layer properties that may affect dry and / or wet etching rates. Alternatively or additionally, it may allow selective deposition on exposed areas relative to unexposed areas, such as region-selective sacrificial masking layer deposition.

[0073] In some embodiments, the radiation-modified layer further comprises one or more elements selected from Sn, Sb, Hf, In, and Te. Alternatively or additionally, elements selected from Sn, Sb, Hf, In, and Te may be provided in the underlying layer on which the radiation-modified layer is deposited. Therefore, in some embodiments, the process for depositing the radiation-modified layer involves depositing the radiation-modified layer on an underlying layer comprising elements selected from Sn, Sb, Hf, In, and Te. Without being bound by any theory or particular mode of operation, these elements are believed to improve the sensitivity of the modifiable layer to EUV radiation through their relatively high capture cross-section for EUV photons.

[0074] In some embodiments of this disclosure, the radiation-modifiable layer 106 may comprise a porous material, such as a microporous and / or nanoporous material, including porous materials such as spin-coated glass (SOG) and spin-coated carbon (SOC). In some embodiments of this disclosure, the radiation-modifiable layer 106 may be provided with one or more sacrificial masking layer materials, including but not limited to boron carbide, amorphous carbon, silicon oxide, silicon nitride, and silicon oxynitride.

[0075] In some embodiments of this disclosure, the radiation-modified layer 106 may comprise a patterned radiation-modified material, such as a patterned resist or a patterned sacrificial masking layer, which includes one or more features. These features may be transferred to the underlying substrate during a subsequent etching process. The features may include any geometry that can be formed depending on the exposure and associated development processes, and may include, but are not limited to, line features, frame features, aperture features, and circular features.

[0076] In some embodiments of this disclosure, the radiation-modified layer 106 may comprise a planar radiation-modified material that can be patterned during subsequent processes after local modification. For example, the radiation-modified layer 106 may comprise a planar resist that can be patterned during subsequent photolithography exposure steps or during the radiation-modified layer 106 itself.

[0077] A substrate 15 may be disposed within a reaction chamber 12 and held in place by a substrate holder 13 configured to hold at least one substrate thereon. In some embodiments of this disclosure, the selective deposition process disclosed herein may utilize a process of heating the substrate 15 and the associated radiation-modified layer 106 to a suitable process temperature. Therefore, the substrate holder 13 may include one or more heating elements 110 configured to heat the substrate 15 on which the radiation-modified layer 106 is disposed.

[0078] The heating element 110 may be configured to heat the substrate 15 to a temperature between 20 and 450°C, preferably between 50 and 150°C, more preferably between 60 and 120°C, and most preferably between 70 and 100°C, for example, 85°C. In some embodiments of this disclosure, the selective deposition apparatus 11 is constructed and arranged to control the pressure in the reaction chamber to a value between 0.001 and 1000 Torr, preferably between 0.1 and 500 Torr, and most preferably between 1 and 100 Torr.

[0079] In some embodiments of this disclosure, the selective deposition apparatus 11 may include a precursor distribution and removal system 14. The precursor distribution and removal system may include a gas delivery system 112, which may further include one or more precursor sources 114A and 114B configured and arranged to provide vapors of multiple precursors and distribute the associated vapors to the reaction chamber 12. The gas delivery system 112 may also include a source container 116 configured to store and distribute purge gas that can be used in a purge cycle of the exemplary selective deposition process described herein. The gas delivery system 112 may also include a reactant source container 118 configured to contain and distribute precursors to the reaction chamber 12 for use in the exemplary selective deposition process described herein. As a non-limiting example, the selective deposition apparatus 11 may include a first precursor source 114A configured and arranged to provide vapors of a first precursor. In some embodiments, the first precursor source 114A may include a first precursor evaporator configured and arranged to evaporate the first precursor.

[0080] In some embodiments, the first precursor source 114A may include a source container configured to store and contain the first precursor under suitable operating conditions. For example, the first precursor may include a solid precursor, a liquid precursor, or a gaseous precursor, and the source container may be configured to store and contain the solid, liquid, or gaseous precursor under suitable operating conditions.

[0081] In some embodiments, the first precursor source may include a first precursor evaporator, which may include one or more controllable heating elements that can heat the first precursor to a suitable operating temperature, thereby controllably evaporating a portion of the first precursor. The evaporated vapor is then distributed to the reaction chamber 12 via suitable means for selective deposition on the radiation-modified layer. In some embodiments, one or more heating elements associated with the first precursor source 114A may be configured to control the vapor pressure of the first precursor. Additionally, a flow controller 120A, such as a mass flow controller (MFC), may be further associated with the first precursor source 114A and configured to control the mass flow rate of the vapor generated by the first precursor source 114A, such as the first precursor evaporator. In addition to the flow controller 120A, a valve 122A, such as a shut-off valve, may also be associated with the first precursor source 114A and may be used to disconnect the first precursor source 114A from the reaction chamber 12, i.e., when the valve 122A is in the closed position, it may prevent the vapor generated by the first precursor source 114A from flowing into the reaction chamber 12.

[0082] In an additional embodiment, the first precursor source 114A may further include a carrier gas input (not shown) such that a carrier gas (e.g., nitrogen) may pass through or bubble through the first precursor, such that the first precursor may become entrained in the carrier gas and the carrier gas / first precursor vapor may subsequently be delivered to the reaction chamber 12 in an appropriate manner.

[0083] In some embodiments of this disclosure, selective deposition apparatus 11 ( Figure 3 The system may include a precursor distribution and removal system 14, which is configured and arranged to supply vapors of a first precursor from a first precursor source 114A to the reaction chamber 12 and to remove vapors of the first precursor from the reaction chamber 12.

[0084] In some embodiments of this disclosure, the selective deposition apparatus 11 may include a precursor dispensing and removal system 14 configured and arranged to provide a vapor of a first precursor from a first precursor source 114A to a reaction chamber 12. This vapor contains elements such as metals or semiconductors, for example, group IV semiconductors. In the reaction chamber 12, the elements such as metals or semiconductors may be selected from aluminum (Al), hafnium (Hf), gallium (Ga), germanium (Ge), silicon (Si), zirconium (Zr), indium (In), lithium (Li), tellurium (Te), antimony (Sb), titanium (Ti), tantalum (Ta), and tin (Sn).

[0085] In some embodiments of this disclosure, the selective deposition apparatus 11 may include a precursor dispensing and removal system 14 configured and arranged to provide a precursor comprising an alkylamide precursor, such as a metal alkylamide precursor or a group IV semiconductor alkylamide precursor, in the reaction chamber 12.

[0086] In some embodiments of this disclosure, the selective deposition apparatus 11 may include a precursor dispensing and removal system 14 configured and arranged to provide a precursor selected from trimethylaluminum (TMA), triethylaluminum (TEA), and dimethylaluminum hydride (DMAH). The selective deposition apparatus may thus selectively provide a metal, such as aluminum, in or on one of the modified and unmodified layer portions, such as a photoresist.

[0087] In some embodiments of this disclosure, the selective deposition apparatus 11 may include a precursor dispensing and removal system 14 configured and arranged to provide vapor of a first precursor from a first precursor source 114 to a reaction chamber 12, wherein the vapor comprises a metal halide or a group IV semiconductor halide.

[0088] In some embodiments of this disclosure, the precursor dispensing and removal system 14 of the selective deposition apparatus 11 is configured and arranged to provide a precursor comprising SnI4 or SnCl4 in the reaction chamber. In some embodiments of this disclosure, the exemplary selective deposition apparatus 11 may include a precursor dispensing and removal system configured and arranged to provide a precursor selected from tetraethyltin, tetramethyltin, or tin acetylacetonate in the reaction chamber. The selective deposition apparatus 11 may thereby selectively provide a metal such as tin in or on one of the modified and unmodified layer portions, such as a resist.

[0089] In some embodiments of this disclosure, an exemplary selective deposition apparatus 11 may include a precursor dispensing and removal system 14 configured and arranged to provide a vapor of a first precursor from a first precursor source 114 to a reaction chamber 12, wherein the vapor comprises a metal or a group IV semiconductor, such as magnesium and / or calcium.

[0090] In some embodiments, the selective deposition apparatus 11 may be configured and arranged to selectively deposit silicon in or on one of the modified and unmodified layer portions, such as a resist.

[0091] In some embodiments, the first precursor source 114A may be configured and arranged to provide a vapor of aminosilane.

[0092] More specifically, the precursor distribution system may include a gas delivery system 112 and one or more gas lines, such as a gas line 124 in fluid communication with a first precursor source 114A, a gas line 126 in fluid communication with a second precursor source 114B, a gas line 128 in fluid communication with a source container 116, and a gas line 130 in fluid communication with a reactant source container 118. As a non-limiting example, gas line 124 is fluidly connected to the first precursor source 114A and may be configured to deliver vapor of the first precursor to the reaction chamber 12.

[0093] The precursor distribution system may also include a gas distributor 132 configured to distribute vapors of the first precursor into the reaction chamber 12 and onto a substrate 15 on which a radiation-modified layer 106 is disposed, the gas distributor 132 being in fluid communication with gas lines 126, 128 and 130 and also with gas line 124.

[0094] As a non-limiting example embodiment, the gas distributor 132 may include spray heads, such as... Figure 3 The image is shown in a box. It should be noted that although the spray head is shown in a box, the spray head can be a relatively complex structure. In alternative embodiments, the spray head may be configured to maintain separation between multiple vapors introduced into the spray head, the multiple vapors contacting each other only in the vicinity of the substrate 15 disposed within the reaction chamber 12. Furthermore, the spray head may be configured to provide a vertical or horizontal airflow into the reaction chamber 12. An exemplary gas distributor is described in U.S. Patent No. 8,152,922, the contents of which are incorporated herein by reference to the extent that they do not contradict this disclosure.

[0095] like Figure 3 As illustrated, the precursor distribution system may include a gas delivery system 112, at least gas lines 124, 126, 128 and 130, and a gas distributor 132; however, it should be noted that the precursor distribution system may include... Figure 3 Other components not shown, such as additional gas lines, valves, actuators, seals, and heating elements.

[0096] In addition to the precursor distribution system, the precursor distribution and removal system 14 of the selective deposition apparatus 11 may also include a removal system configured and arranged to remove gas from the reaction chamber 12. In some embodiments, the removal system may include an exhaust port 134 disposed within the wall of the reaction chamber 12, an exhaust line 136 in fluid communication with the exhaust port 134, and a vacuum pump 138 in fluid communication with the exhaust line 136 and configured to evacuate air from the reaction chamber 12. After the gas has been evacuated from the reaction chamber 12 using the vacuum pump 138, the gas may be conveyed along an additional exhaust line 140 and exit an additional station 11, where it may undergo further elimination processes.

[0097] To further aid in the removal of precursor gases (i.e., reactive vapors) from reaction chamber 12, the removal system may further include a source container 116 fluidly connected to gas distributor 132 via gas line 128. For example, source container 116 may be configured to contain and store purge gases, such as argon (Ar), nitrogen (N2), or helium (He). Flow controller 120C and valve 122C associated with source container 116 control the flow rate, particularly the mass flow rate of the purge gas delivered via gas line 128 to gas distributor 132 and into reaction chamber 12, whereby the purge gas helps remove gaseous precursor gases, inert gases, and byproducts from reaction chamber 12, particularly from the exposed surfaces of the modifiable layer 106. The purge gas (and any associated precursors and byproducts) may exit reaction chamber 12 via exhaust port 134 using vacuum pump 138.

[0098] In some embodiments of this disclosure, the selective deposition apparatus 11 may further include a sequence controller 142 operatively connected to the precursor dispensing system and the removal system and including a memory 144 provided with a program to perform selective deposition on or in one of the radiation-modified and unmodified layers when the sequence controller is run.

[0099] Sequence controller

[0100] More specifically, the exemplary selective deposition apparatus 11 may include a sequence controller 142, which may further include control lines 144A, 144B, and 144C, wherein the control lines enable communication between various systems and / or components of the selective deposition apparatus 11 and the sequence controller 142. For example, control line 144A enables the sequence controller 142 to communicate with a gas delivery system 112, thereby providing control over a precursor distribution system including gas lines 124, 126, 128, and 130 and a gas distributor 132. Control line 144B enables the sequence controller 142 to communicate with a reaction chamber 12, thereby providing control over the operation of the reaction chamber, including but not limited to process pressure and substrate stage 13 temperature. Control line 144C enables the sequence controller 142 to communicate with a vacuum pump 138, such that the sequence controller 142 can provide operation and control over a gas removal system. The sequence controller 142 may be operatively connected to a control system 8 (in... Figure 2 middle).

[0101] It should be pointed out that, such as Figure 3 As illustrated, the sequence controller 142 includes three control lines 144A, 144B, and 144C; however, it should be understood that a large number of control lines (i.e., control lines with electrical and / or optical connections) may be used to connect the desired systems and components, including the selective deposition apparatus 11, to the sequence controller 142, thereby providing overall control of the apparatus.

[0102] In some embodiments of this disclosure, the sequence controller 142 may include electronic circuitry for selectively operating valves, heaters, flow controllers, manifolds, pumps, and other devices included in the exemplary selective deposition apparatus 11. Such circuitry and components are used to introduce precursor gas and purge gas from respective precursor sources 114A, 114B, reactant source container 118, and purge gas source container 116. The sequence controller 142 may also control the timing of the precursor pulse sequence, the temperature of the substrate and reaction chamber 12, and the pressure of the reaction chamber, as well as various other operations necessary to provide proper operation of the selective deposition apparatus 11. In some embodiments, the sequence controller 142 may also include control software and electrically or pneumatically controlled valves to control the flow of precursor and purge gas into and out of the reaction chamber 12. In some embodiments of this disclosure, the sequence controller 142 may include a memory 144 provided with programs to perform selective deposition on or in a radiation-modifiable layer when run on the sequence controller. For example, the sequence controller 142 may include modules, such as software or hardware components, like an FPGA or ASIC, to perform certain selective deposition processes. The module can be configured to reside on an addressable storage medium of the sequential controller 142 and can be configured to perform one or more selective deposition processes.

[0103] In some embodiments of this disclosure, the memory 144 of the sequence controller 142 may be provided with a program that performs the following operations to produce a sacrificial masking layer by providing a precursor in the reaction chamber selected to react with one of the modified and unmodified layer portions but not with the other of the modified and unmodified layer portions: enabling a precursor dispensing system and a removal system to provide vapor of the precursor to the radiation-modified layer 106 on the substrate 15 within the reaction chamber 12, whereby the precursor selectively reacts with one of the modified and unmodified layer portions of the radiation-modified layer 106 on the substrate 15.

[0104] In some embodiments of this disclosure, the exemplary selective deposition apparatus 11 may include a second precursor source 114B, such as a second precursor evaporator. More specifically, the second precursor source 114B may be configured and arranged to provide vapor of a second precursor. For example, the second precursor source 114B may include a second precursor evaporator configured and arranged to evaporate a second precursor. In some embodiments, the second precursor source 114B may be the same as or substantially the same as the first precursor source 114A, and therefore details regarding the second precursor source 114B are omitted for brevity.

[0105] In some embodiments, the precursor distribution and removal system 14 may be configured and arranged to provide vapor of a second precursor from a second precursor source 114B to the reaction chamber 12. For example, a gas line 126 may be fluidly connected to the second precursor source 114B via a flow controller 120B and a valve 122B, and may deliver vapor of the second precursor from the second precursor source 114B to a gas distributor 132 and subsequently to the reaction chamber 12. In some embodiments, a program in memory 144 may be programmed, when run on a sequence controller 142, to perform selective deposition on or in the radiation-modified layer 106 by activating the precursor distribution and removal system to provide vapor of the second precursor to the reaction chamber 12, whereby the second precursor may react in the reaction chamber with one of the modified and unmodified layer portions 106 but not with the other of the modified and unmodified layer portions to create a sacrificial masking layer on the substrate 15.

[0106] In some embodiments of this disclosure, the program in memory 144 is programmable to perform selective deposition on the radiation-modified layer 106 when run on sequence controller 142 by enabling a precursor dispensing system and a removal system to provide a second precursor after a first precursor, i.e., a first precursor source 114A may provide vapor of the first precursor to reaction chamber 12 and selectively deposit the first precursor on or in the radiation-modified layer 106, and subsequently a second precursor source 114B may provide vapor of the second precursor to reaction chamber 12 and selectively deposit the second precursor on or in the radiation-modified layer 106. When run on sequence controller 142, the selective deposition cycle of the program stored in memory 144 may have a first period of providing vapor of the first precursor longer than a third period of providing vapor of the second precursor to perform selective deposition on or in the radiation-modified layer 106.

[0107] In some embodiments, the sequence controller 142 may run a program on the memory 144 to enable a precursor dispensing system and a removal system to provide a first precursor after a second precursor. Specifically, the second precursor source 114B may provide vapor of the second precursor to the reaction chamber 12 for selective deposition on the radiation-modifiable layer 106, and subsequently the first precursor source 114A may provide vapor of the first precursor to the reaction chamber 12 for selective deposition on the modifiable layer 106.

[0108] In some embodiments of this disclosure, a program stored in memory 144 is programmed to perform selective deposition on the radioactive modified layer 106 when running on sequence controller 142 by: enabling a precursor dispensing system and a removal system to provide a first precursor to reaction chamber 12, then performing a purge cycle to remove excess of the first precursor and any byproducts from the reaction chamber, subsequently providing a second precursor to the reaction chamber, and then performing a second purge cycle to remove excess of the second precursor and any byproducts from the reaction chamber.

[0109] More specifically, the program in the memory 144 of the sequence controller 142 can first enable the first precursor source 114A and supply vapor of the first precursor to the reaction chamber 12 for selective deposition on or in the radiation-modified layer 106. Subsequently, the first precursor source 114A can be deactivated and the fluid connection between the first precursor source 114A and the reaction chamber 12 can be disconnected, for example, via valve 122A associated with the first precursor source 114A. After the first precursor source 114A is deactivated and disconnected from the reaction chamber 12, the program in the memory 144 of the sequence controller 142 can engage or continue engaging the vacuum pump 138 to remove excess vapor of the first precursor and any byproducts from the reaction chamber 12. In another embodiment, in addition to using a vacuum pump 138 to remove excess vapor and any byproducts of the first precursor from the reaction chamber 12, a program stored in a memory 144 of the sequence controller 142 can also activate the source container 116, which contains a purge gas source, for example, by opening a valve 122C associated with the source container 116. The purge gas can flow through a gas line 128 and enter the reaction chamber 12 via a gas distributor 132 to purge the reaction chamber 12, specifically purging the modifiable layer 106 disposed on the substrate 15. The program stored in the memory 144 of the sequence controller 142 can then stop the flow of the purge gas through the reaction chamber 12 and subsequently activate the second precursor source 114B, thereby providing vapor of the second precursor to the reaction chamber 12, particularly selectively depositing the second precursor vapor provided by the second vapor source 114B onto the radiation-modifiable layer 106. The program installed in the memory 144 of the sequence controller 142 can then stop the flow of vapor from the second precursor to the reaction chamber 12 and then activate the source container 116 to purge the reaction chamber again, for example, to remove excess vapor from the second precursor.

[0110] In some embodiments of this disclosure, a program stored in memory 144 is programmed to perform selective deposition on or in the radioactive modified layer 106 by, when run on sequence controller 142, the following operations: enabling a precursor distribution system and a removal system to supply vapor of a second precursor to the reaction chamber, then performing a purge cycle to remove excess vapor of the second precursor and any byproducts from the reaction chamber, subsequently supplying vapor of a first precursor to the reaction chamber, and then performing a second purge cycle to remove excess vapor of the first precursor and any byproducts from the reaction chamber.

[0111] In other embodiments of this disclosure, in addition to the first precursor source 114A and the second precursor source 114B, the exemplary additional station 11 may further include a reactant source container 118 and a reactant supply line, i.e., a gas line 130, which is configured and arranged to provide reactants containing oxygen precursors to the reaction chamber 12.

[0112] In some embodiments of this disclosure, reactant source container 118 may include reactants in a solid, liquid, or gas phase. In some embodiments, reactant source container 118 may include a reactant evaporator, i.e., one or more heating elements may be associated with the reactant source container to achieve evaporation of the reactants and thereby provide vaporized reactants, including oxygen precursors, to the reaction chamber 12.

[0113] In some embodiments, the flow of vaporized reactants, including oxygen precursors, into the reaction chamber can be controlled by using both a valve 122D and a flow controller 120D associated with the reactant source container 118. In some embodiments of this disclosure, where the reactant source container 118 further includes a reactant evaporator, the reactant evaporator may be constructed and arranged to evaporate at least one of water (H2O) or hydrogen peroxide (H2O2) as a reactant including oxygen precursors.

[0114] In some embodiments of this disclosure, reactant source container 118 may store gaseous oxygen precursor and distribute the gaseous oxygen precursor to reaction chamber 12 via reactant supply line 130 and gas distributor 132. In some embodiments, the gaseous oxygen precursor may include at least one of ozone (O3) or molecular oxygen (O2).

[0115] In some embodiments of this disclosure, the exemplary selective deposition apparatus 11 may optionally further include a plasma generator 146. The plasma generator 146 may be configured and arranged to generate plasma from a gaseous oxygen precursor, thereby providing one or more of atomic oxygen, oxygen ions, oxygen radicals, and stimulated oxygen species to the reaction chamber 12, whereby the oxygen-based plasma generated by the plasma generator 146 can react with the layer 106 disposed above the substrate 15.

[0116] In some embodiments, a purge cycle may be performed after each step in the program sequence to remove excess precursors and byproducts from the reaction chamber 12 by purging the reaction chamber 12 using a vacuum pump 138 and optionally circulating purge gas from the source container 116. In some embodiments, the program sequence of providing an oxygen precursor followed by a vapor of a first precursor may be repeated once or multiple times. In some embodiments, a purge cycle may be performed after each step in the program sequence to remove excess precursors and byproducts from the reaction chamber 12 by purging the reaction chamber 12 using a vacuum pump 138 and optionally circulating purge gas from the source container 116.

[0117] In some embodiments of this disclosure, the program in memory 144 is programmed to perform selective deposition on or in layer 106 by, when running on sequence controller 142, enabling a precursor distribution system and a removal system to provide a first precursor, followed by a reactant, followed by a second precursor, and then a reactant.

[0118] In some embodiments of this disclosure, the program in memory 144 is programmable to perform selective deposition on or in layer 106 by multiple operations when running on sequence controller 142: enabling precursor distribution system and removal system 14 to provide a first precursor, followed by providing a reactant, followed by providing a second precursor, and subsequently providing a reactant.

[0119] In some embodiments of this disclosure, the program in memory 144 is programmable to perform selective deposition on or in layer 106 when running on sequence controller 142 by enabling a precursor dispensing system and a removal system to remove the precursor and / or reactant from the reaction chamber between each of the steps of providing a first precursor, subsequently providing a reactant, subsequently providing a second precursor, and subsequently providing a reactant.

[0120] In some embodiments of this disclosure, the program in memory 144 is programmable to perform selective deposition on or in layer 106 by, when run on sequence controller 142, activating a precursor dispensing system and a removal system to provide a first precursor, followed by a second precursor, and subsequently a reactant. In some embodiments, the sequence of providing the first precursor, followed by the second precursor, and subsequently the reactant may be repeated once or multiple times. In some embodiments, a purge cycle may be performed after each step in the sequence to remove excess precursors and byproducts from the reaction chamber 12 by purging the reaction chamber 12 using vacuum pump 138 and optionally by allowing purge gas from source container 116 to flow.

[0121] In some embodiments of this disclosure, the program in memory 144 is programmable to perform selective deposition on or in layer 106 when run on sequence controller 142 by enabling a precursor dispensing system and a removal system to provide a second precursor, followed by providing a first precursor, and subsequently providing a reactant. In some embodiments, the sequence of providing the second precursor, followed by the first precursor, and subsequently the reactant may be repeated once or multiple times. In some embodiments, a purge cycle may be performed after each step in the sequence to remove excess precursors and byproducts from the reaction chamber 12 by purging the reaction chamber 12 using vacuum pump 138 and optionally by allowing purge gas from source container 116 to flow.

[0122] In some embodiments of this disclosure, the program in memory 144 is programmable to perform selective deposition on or in layer 106 when run on sequence controller 142 by enabling a precursor dispensing system and a removal system to provide a first precursor, followed by a reactant, and then a second precursor. In some embodiments, the sequence of providing the first precursor, followed by the reactant, and then the second precursor may be repeated once or multiple times. In some embodiments, a purge cycle may be performed after each step in the sequence to remove excess precursors and byproducts from the reaction chamber 12 by purging the reaction chamber 12 using vacuum pump 138 and optionally by allowing purge gas from source container 116 to flow.

[0123] In some embodiments of this disclosure, the program in memory 144 is programmable to perform selective deposition on or in layer 106 when run on sequence controller 142 by: enabling a precursor dispensing system and a removal system to provide reactants, followed by providing a first precursor, followed by providing a second precursor, and subsequently providing reactants. In some embodiments, the sequence of providing reactants, followed by providing the first precursor, followed by providing the second precursor, and subsequently providing reactants may be repeated once or multiple times. In some embodiments, a purge cycle may be performed after each step in the sequence to remove excess precursors and byproducts from the reaction chamber by purging the reaction chamber 12 using vacuum pump 138 and optionally circulating purge gas from source container 116.

[0124] In some embodiments of this disclosure, the program in memory 144 is programmable to perform selective deposition on or in layer 106 when run on sequence controller 142 by: enabling a precursor dispensing system and a removal system to provide reactants, followed by providing a first precursor, then providing reactants again, and then providing a second precursor. In some embodiments, the sequence of providing reactants, followed by providing the first precursor, then providing reactants again, and then providing the second precursor may be repeated once or more. In some embodiments, a purge cycle may be performed after each step in the sequence to remove excess precursors and byproducts from the reaction chamber by purging the reaction chamber 12 using vacuum pump 138 and optionally circulating purge gas from source container 116.

[0125] Figure 4 This illustration shows a resist-free patterning method according to an embodiment of the present disclosure. Figure 1 The figure shows a radiation-modified layer (410) deposited on a substrate (430). As shown, an optional underlayer (420) may be provided between the substrate (430) and the radiation-modified layer (410). In some embodiments, the radiation-modified layer (410) may be formed by the surface of the underlayer (420). It should be understood that in other embodiments, the radiation-modified layer (410) may be deposited directly on the substrate, thereby avoiding the need for an underlayer (420). Figure 2 This illustrates how a radiation-modified layer (410) can be exposed to extreme ultraviolet (EUV) radiation, thereby producing multiple radiation-modified layer portions (411) and multiple unmodified layer portions (412). Then, it can be... Figure 3 b) shows the radiation-modified layer portion (411) or as small Figure 3 As shown in a), a sacrificial masking layer is selectively deposited on the unmodified layer portion (412). Subsequent etching steps result in the formation of recesses (450), such as small... Figure 4 As shown in a and 4b. In particular, small Figure 4 b illustrates how a recess (450) is etched under the unmodified layer portion (412) when a sacrificial masking layer (440) has been deposited on the radiation-modified layer portion (411). Figure 4 a illustrates how a recess (450) is etched beneath a radiation-modified layer portion (411) when a sacrificial masking layer (440) is deposited on an unmodified layer portion (412). Optionally, the sacrificial masking layer deposition step and the etching step can be performed in the same reaction chamber. Optionally, any sacrificial masking layer removal step can also be performed in the same reaction chamber.

[0126] Figure 5 This illustration shows a resist-free patterning method according to an embodiment of the present disclosure. Figure 1The diagram shows a radiation-modified layer (410) deposited on a substrate (430). The radiation-modified layer (410) may contain organic compounds comprising C, N, H and / or O, and may be locally modified by means of photons such as extreme ultraviolet (EUV) photons. This can result in a localized change in the etching rate toward a wet or dry etching process.

[0127] As shown, an optional lower layer (420) may be provided between the substrate (430) and the radiation-modified layer (410). In some embodiments, the radiation-modified layer (410) may be formed from the surface of the lower layer (420). It should be understood that in other embodiments, the radiation-modified layer (410) may be deposited directly on the substrate, thereby avoiding the need for the lower layer (420). Figure 2 This illustrates how a radiation-modified layer (410) can be exposed to extreme ultraviolet (EUV) radiation, thereby producing multiple radiation-modified layer portions (411) and multiple unmodified layer portions (412). Figure 3 This illustrates how the unmodified layer portion (412) is removed during the layer removal step while the radiation-modified layer portion (411) remains in place. In an alternative embodiment (not shown), the unmodified radiation-modified layer portion is unaffected by the layer removal step and thus remains in place, while the radiation-modified layer portion (411) is removed during the layer removal step.

[0128] In small Figure 3 Following the etching step, a sacrificial masking layer can be selectively deposited. The sacrificial masking layer can be, for example, a small... Figure 4 a) shows the deposition on the radiation-modified layer portion (411), or as shown in small Figure 4 The deposition shown in b) is on the exposed underlying layer. In the absence of an underlying layer, the sacrificial masking layer can be deposited directly on the substrate (430) (example not shown). When the radiation-modified layer portion is removed during the layer removal step while the unmodified layer portion remains in place, the sacrificial masking layer can be deposited on the unmodified layer portion (example not shown).

[0129] An etching step can then be performed after the deposition of the sacrificial masking layer, which results in the formation of recesses (450) in areas where the sacrificial masking layer has not yet been deposited, such as, for example, small... Figure 5 As shown in a and 5b. In particular, small Figure 5 a shows how to etch a recess (450) at the location of the unmodified layer portion (411) when a sacrificial masking layer (440) has been deposited on the radiation-modified layer portion (411). Figure 5b illustrates how a recess (450) is etched at the location of the radiation-modified layer portion (412) when a sacrificial masking layer (440) has already been deposited on the unmodified layer portion (412). Of course, the same principle applies to other embodiments: etching areas where the sacrificial masking layer has not yet been deposited during the etching step, and not etching or substantially not etching areas where the sacrificial masking layer has been deposited during the etching step. If necessary, the sacrificial masking layer can be removed after the etching step. Optionally, the sacrificial masking layer deposition step and the etching step can be performed in the same reaction chamber. Optionally, any sacrificial masking layer removal step can also be performed in the same reaction chamber.

[0130] Suitable radiation-modified layers (410) include amorphous carbon layers, such as those deposited by plasma-enhanced atomic layer deposition (PEALD) or plasma-enhanced chemical vapor deposition (PECVD). The amorphous carbon layer may contain sp2 and sp3 carbon. In other words, the amorphous carbon layer may contain C=C, C=C, and CH bonds. Additionally, the amorphous carbon may contain CN and / or CO bonds. When regions in the amorphous carbon layer are exposed to EUV light, the C=C, CH, CN, and / or CO bonds may be disrupted. Without being bound by any particular theory or mode of operation, it is believed that the resulting damage may allow the exposed portions of the amorphous carbon layer to be selectively etched by H radicals at low temperatures, such as below 100°C, below 90°C, below 80°C, below 70°C, below 60°C, below 50°C, or below 40°C. H radicals may be generated, for example, in a remote plasma tool. It is believed that the unexposed amorphous carbon layer portions are not etched by H radicals at these low temperatures because these portions are not damaged by EUV exposure, and because the C-C bonds in the amorphous carbon are essentially not etched by H radicals. Furthermore, and without being bound by any particular theory or operating mode, it is believed that H radicals can hydrogenate the surface of the amorphous carbon layer, resulting in the formation of CH3-terminated groups on said surface. Therefore, it is believed that regions with CH3-terminated amorphous carbon can thus be formed, which can be used as a barrier layer or active layer during the deposition of a sacrificial masking layer.

[0131] An example of a sacrificial masking layer that can be selectively deposited on CH3-terminated amorphous carbon is RuO2, for example, initiated in an organic solvent by means of a precursor containing RuO4. Compositions containing RuO4 in organic solvents are commercially available.

[0132] Examples of masking layers that can be selectively deposited on the underlying layer or substrate rather than on CH3-terminated amorphous carbon include TiO (i.e., titanium oxide). x TiO x C y(i.e., titanium oxide) or TiN is deposited using atomic layer deposition with titanium halide precursors such as TiCl4; hafnium oxide is deposited using atomic layer deposition with hafnium halide precursors such as HfCl4; and ruthenium is deposited using atomic layer deposition with EBECHRu. These materials can be selectively deposited on CH3-terminated amorphous carbon as underlayers and substrates, including metal-based underlayers and silicon-based underlayers and substrates such as single-crystal silicon, spin-coated silicon, and low-k dielectrics. When the masking layer is selected from titanium oxide, titanium nitride, and ruthenium, suitable underlayers for selective deposition with respect to CH3-terminated amorphous carbon may include SiO2, SiN, and / or SiON. When the masking layer is selected from titanium oxide or titanium nitride, suitable underlayers for selective deposition with respect to CH3-terminated amorphous carbon may include ruthenium. When ruthenium is used as the masking layer, suitable underlayers for selective deposition with respect to CH3-terminated amorphous carbon may include titanium oxide or titanium nitride. In some embodiments, the aforementioned lower layer may additionally contain tin, which can reduce the EUV dose required to achieve proper exposure.

[0133] When used for deposition, etching, and / or other purposes, the methods and apparatus of the present invention will offer numerous advantages. For example, problems associated with resist collapse can be avoided. Conversely, prior art techniques employing thick resist lines (e.g., 30 nm thick) may experience resist line collapse during wet development when the adhesion between the resist and the underlying layer is insufficient. Additionally, the methods disclosed herein will avoid problems such as PAG segregation and PAG quenching that can occur when using resists containing photoacid generators (PAGs). Furthermore, when used for etching purposes, the methods of the present invention will allow for the selective deposition of sacrificial masking layers with excellent etch budgets, even when only very thin underlying layers are required and very high resolution is provided, such as 13 nm, or even approximately 8 nm resolution when using high numerical apertures.

[0134] The exemplary embodiments described above do not limit the scope of the invention, as these embodiments are merely examples of embodiments of the invention, which is defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to be included within the scope of the invention. In fact, various modifications to this disclosure, such as alternative combinations of the described elements, will be apparent to those skilled in the art from the specification, in addition to those shown and described herein. Such modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

1. A substrate processing apparatus for producing a sacrificial masking layer on a substrate, the apparatus comprising: A photolithography input / output port, which is used to transfer a substrate between the substrate processing apparatus and the photolithography projection apparatus; A modifiable layer deposition apparatus is used to deposit a radiation-modifiable layer on a substrate, wherein the radiation-modifiable layer is a self-assembled monolayer (SAM). A selective deposition apparatus for providing a first precursor in a reaction chamber that is selectively reacted with one of the radiation-modified and unmodified layer portions but not with the other of the radiation-modified and unmodified layer portions to produce the masking layer; A substrate loader for transferring a substrate between the lithography input / output port and the selective deposition apparatus; and, A control system, operably connected to the substrate loading / unloading device and the selective deposition apparatus, and having a memory provided with a program that, when executed on the control system, performs the following: Control the substrate loader to pick up the substrate via the lithography input / output port and move it to the selective deposition apparatus; and The selective deposition apparatus is controlled to provide a first precursor, selected to react with one of the radiation-modified and unmodified layer portions but not with the other of the radiation-modified and unmodified layer portions, in the reaction chamber to deposit the sacrificial masking layer on one of the radiation-modified and unmodified layer portions, the sacrificial masking layer comprising an element selected from metals, silicon (Si), and germanium (Ge).

2. The substrate processing apparatus of claim 1, wherein the memory is provided with a program that, when executed on the control system, enables a precursor dispensing and removal system to remove a portion of the first precursor from the reaction chamber after the first precursor has been provided to the reaction chamber.

3. The substrate processing apparatus of claim 2, wherein the precursor dispensing and removal system includes one or more reaction chamber valves for providing a gaseous second precursor to and removing a gaseous second precursor from the reaction chamber, and the selective deposition process stored in the memory further includes enabling the precursor dispensing and removal system to provide the second precursor in the reaction chamber to react in the reaction chamber with one of the modified and unmodified layer portions without reacting with the other of the modified and unmodified layer portions to produce the sacrificial masking layer.

4. The substrate processing apparatus of claim 3, wherein the selective deposition process stored in the memory further includes enabling the precursor dispensing and removal system to remove a portion of the second precursor from the reaction chamber.

5. The substrate processing apparatus of claim 1, wherein the precursor dispensing and removal system of the selective deposition apparatus is configured and arranged to provide metal halides in the reaction chamber.

6. The substrate processing apparatus of claim 1, wherein the precursor dispensing and removal system of the selective deposition apparatus is configured and arranged to provide a precursor comprising a metal or semiconductor in the reaction chamber, the metal or semiconductor being selected from aluminum (Al), hafnium (Hf), gallium (Ga), germanium (Ge), zirconium (Zr), indium (In), lithium (Li), tellurium (Te), antimony (Sb), titanium (Ti), tantalum (Ta), tungsten (W), and tin (Sn).

7. The substrate processing apparatus of claim 1, wherein the precursor dispensing and removal system of the selective deposition apparatus is configured and arranged to provide a precursor containing an oxidant in the reaction chamber.

8. The substrate processing apparatus of claim 1, wherein the precursor dispensing and removal system of the selective deposition apparatus is configured and arranged to provide a silicon-containing precursor in the reaction chamber.

9. The substrate processing apparatus of claim 1, wherein the selective deposition equipment is configured and arranged to control the temperature of the reaction chamber to a value between 20 and 450°C.

10. The substrate processing apparatus of claim 1, wherein the selective deposition equipment is configured and arranged to control the pressure in the reaction chamber to a value between 0.001 and 1000 Torr.

11. The substrate processing apparatus of claim 10, wherein the selective deposition apparatus is configured and arranged to control the pressure in the reaction chamber to a value between 0.1 and 500 Torr.

12. The substrate processing apparatus of claim 11, wherein the selective deposition equipment is configured and arranged to control the pressure in the reaction chamber to a value between 1 and 100 Torr.

13. The substrate processing apparatus of claim 1, wherein the radiation-modified layer deposition apparatus includes a rotatable substrate stage for rotating the substrate and a liquid dispenser for supplying liquid to the surface of the substrate.

14. The substrate processing apparatus according to claim 1, wherein the apparatus comprises: Wafer fab input / output ports, which are used to transfer substrates between the substrate processing apparatus and the semiconductor wafer fab; and A control system, operably connected to the substrate loading / unloading device, the radiation-modified layer deposition apparatus, and the selective deposition apparatus, and provided with a memory containing a program that, when executed on the control system, performs the following: Control the substrate loader to pick up the substrate from the wafer fab input / output port and move it to the modifiable layer deposition equipment; Control the modifiable layer deposition apparatus to deposit a radiation-modifiable layer on the substrate; and, The substrate handler is controlled to pick up the substrate from the modifiable layer deposition apparatus and move it to the photolithography projection apparatus via the photolithography input / output port; and after the radiation-modifiable layer on the substrate is locally modified with the exposed radiation of the photolithography projection apparatus: Control the substrate loader to pick up the substrate via the lithography input / output port and move it to the selective deposition apparatus; The selective deposition apparatus is controlled to provide a first precursor in the reaction chamber, selected to react with one of the radiation-modified and unmodified layer portions but not with the other of the radiation-modified and unmodified layer portions, to produce the sacrificial masking layer; and, Control the substrate loader to pick up the substrate from the selective deposition equipment and move it to the wafer fab input / output port.

15. A substrate fabrication method for producing a sacrificial masking layer, the method comprising: A radiation-enhancing layer is deposited on a substrate, wherein the radiation-enhancing layer is a self-assembled monolayer (SAM). The substrate having a radiation-modified layer is provided to a photolithography projection apparatus to locally modify the radiation-modified layer; The radiation-modified layer of the substrate is locally modified by the exposure radiation of the photolithography projection apparatus to modify the radiation-modified layer exposed to radiation. The substrate is moved from the photolithography projection device to the reaction chamber of the selective deposition apparatus; and, A first precursor, selected to react with one of the modified and unmodified layer portions but not with the other, is provided in the reaction chamber to deposit the sacrificial masking layer on one of the radiation-modified and unmodified layer portions, the sacrificial masking layer comprising an element selected from metals, silicon (Si), and germanium (Ge).

16. The substrate processing method according to claim 15, wherein the radiation-modified layer has a thickness between 0.1 and 20 nm.

17. The substrate processing method according to claim 16, wherein the radiation-modified layer has a thickness between 1 and 20 nm.

18. The substrate processing method of claim 15, wherein after providing the first precursor selected to react with one of the modified and unmodified layer portions, a precursor dispensing and removal system removes unreacted portions and / or reaction byproducts of the first precursor from the reaction chamber.

19. The substrate processing method of claim 18, wherein after a portion of the first precursor is removed from the reaction chamber, the precursor dispensing and removal system provides a second precursor to the reaction chamber.

20. The substrate processing method of claim 19, wherein after the second precursor is provided, the precursor dispensing and removal system removes unreacted portions and / or reaction byproducts of the second precursor from the reaction chamber.

21. A substrate processing method for producing a patterned substrate, the method comprising: The substrate processing method according to claim 15 produces a sacrificial masking layer; The substrate is etched through the sacrificial masking layer; as well as, Remove the sacrifice masking layer.

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