Substrate processing apparatus and method

Abstract

To provide a substrate processing method and apparatus for creating a sacrificial masking layer.SOLUTION: The layer is created by providing a first precursor in a reaction chamber, the first precursor selected to react with one of a radiation modified layer portion and an unmodified layer portion on a substrate and to not react with the other of the radiation modified and unmodified layer portions, thereby selectively growing the sacrificial masking layer.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] SUMMARY The present disclosure relates generally to substrate processing equipment and methods for creating sacrificial masking layers.

[0002] A substrate processing apparatus for creating a sacrificial masking layer on a substrate may comprise a litho input / output port for transporting the substrate between the substrate processing apparatus and a lithographic projection apparatus.

[0003] The method of treating a substrate to create a sacrificial masking layer comprises: Providing a substrate having a radiation-modifiable layer in a lithographic projection apparatus for patterning; patterning the radiation-modifiable layer of the substrate with exposure radiation of a lithographic projection apparatus to modify the radiation-modifiable layer upon exposure to the radiation. [Background technology]

[0004] Substrate processing equipment (e.g., a track or coater) can be used to perform other processing steps on the substrate before and / or after forming a pattern in the resist layer on the substrate. For example, if contaminants are present on the substrate, they can be removed by chemical processing. The substrate can be heated to a temperature sufficient to drive off moisture that may be present on the substrate. An adhesion promoter can be applied to promote adhesion of the resist onto the substrate.

[0005] In a resist deposition apparatus of a substrate processing apparatus, a substrate can be covered with a layer of resist, for example, by spin-coating the resist. A viscous resist solution can be dispensed onto the substrate, and the substrate can be spun to form a thin uniform layer. The resist-coated wafer can then be baked to evaporate the resist solvent.

[0006] The substrate with the resist layer can be transferred from the substrate processing equipment to a lithographic projection apparatus. In the lithographic projection apparatus the substrate with the resist layer can be exposed to a patterned radiation beam of (extreme) ultraviolet light. The exposure to radiation induces chemical changes in the resist layer that pattern the layer.

[0007] For EUV lithography, the resist layer can be very thin, and such a thin layer may not be very etch resistant. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Pat. No. 10,343,186 [Patent Document 2] U.S. Patent No. 8,152,922 Summary of the Invention [Means for solving the problem]

[0009] This Summary is provided to introduce a selection of concepts in a simplified form that are described in further detail below in the Detailed Description of Exemplary Embodiments of this Disclosure. This Summary 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.

[0010] In some embodiments, a substrate processing apparatus may be provided for producing a sacrificial masking layer on a substrate. The substrate processing apparatus may include a lithography input / output port for transporting the substrate between the substrate processing apparatus and the lithographic projection apparatus. The substrate processing apparatus may be provided with a selective deposition apparatus for providing a first precursor selected to react with one of the radiation modified layer portion and the unmodified layer portion and not react with the other of the radiation modified layer portion and the unmodified layer portion in the reaction chamber to produce the sacrificial masking layer. The apparatus may include a substrate handler for transporting the substrate between the lithography input / output port and the selective deposition apparatus. The apparatus may include a control system operably coupled to the substrate handler and the selective deposition apparatus. The control system can include a memory comprising a program, which when executed on the control system, controls the substrate handler to pick up the substrate from the lithography input / output port and move it to the selective deposition apparatus, and controls the selective deposition apparatus to supply into the reaction chamber a first precursor selected to react with one of the radiation modified layer portion and the unmodified layer portion and not react with the other of the radiation modified layer portion and the unmodified layer portion to create a sacrificial masking layer.

[0011] In some embodiments, a substrate processing method for producing a sacrificial masking layer is disclosed. The substrate processing method can include providing a substrate having a radiation-modifiable layer to a lithographic projection apparatus for patterning. The substrate processing method further includes patterning the radiation-modifiable layer of the substrate with exposure radiation of the lithographic projection apparatus to modify the radiation-exposed radiation-modifiable layer. The substrate can be transferred from the lithographic projection apparatus to a reaction chamber of a selective deposition apparatus. To produce the sacrificial masking layer, a first precursor can be provided in the reaction chamber, selected to react with one of the modified layer portion and the unmodified layer portion and not react with the other of the modified layer portion and the unmodified layer portion.

[0012] For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention have been described herein above. Of course, it should be understood that not all such objects or advantages may be achieved by any particular embodiment of the invention. Thus, for example, one skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught or suggested herein, without necessarily achieving other objects or advantages as may be taught or suggested herein.

[0013] All of these embodiments are intended to be within the scope of the invention disclosed herein. These and other embodiments will become readily 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.

[0014] While the specification concludes with claims particularly pointing out and distinctly claiming what are regarded as embodiments of the present disclosure, the advantages of the embodiments of the present disclosure may be more readily ascertained from the following description of certain specific examples of embodiments of the present disclosure when read in conjunction with the accompanying drawings. [Brief description of the drawings]

[0015] [Figure 1] 1 is a method of treating a substrate according to at least one embodiment of the present disclosure. [Diagram 2] This is a substrate treatment apparatus suitable for the substrate treatment method of FIG. [Diagram 3] 3 is a selective deposition apparatus for the substrate processing apparatus of FIG. 2. [Figure 4] 1 is a resist patterning method according to an embodiment of the present disclosure. [Diagram 5] 1 is a resist patterning method according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Although certain specific embodiments and examples are disclosed below, it will be understood by those skilled in the art that the present invention extends beyond the specifically disclosed embodiments and / or applications of the present invention, as well as obvious modifications and equivalents thereof. Therefore, it is intended that the scope of the disclosed invention should not be limited by the specific disclosed embodiments described below. The figures shown in this specification are not meant to be actual drawings of any particular materials, structures or devices, but are merely idealized representations used to describe the embodiments of the present disclosure.

[0017] As used herein, the term "substrate" may refer to any underlying material or materials that may be used or on which a device, circuit or film may be formed. Additionally, the term "modifiable layer" may refer to any material into which additional species, such as atoms, molecules, or ions, may be introduced. The term "semiconductor device structure" may refer to any portion of a processed or partially processed semiconductor structure that is, contains, or defines at least a portion of an active or passive component of a semiconductor device formed on or in a semiconductor substrate. For example, semiconductor device structures may include active and passive components of an integrated circuit, such as transistors, memory elements, transducers, capacitors, resistors, conductive lines, conductive vias, conductive contact pads, and the like.

[0018] As used herein, the term "precursor" can refer to a compound that participates in a chemical reaction that produces another compound, and specifically a compound that constitutes the matrix or backbone of the membrane. The term "reactant" can be used interchangeably with the term precursor. Precursors 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 depending on the situation.

[0019] The term "atomic layer deposition" can refer to a deposition process in which deposition cycles, typically multiple successive deposition cycles, are performed in a process chamber. The term atomic layer deposition as used herein is also meant to include processes indicated by related terms, such as chemical vapor deposition atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, or metalorganic MBE, and chemical beam epitaxy, when performed with alternating pulses of precursor / reactive gases and purge (e.g., inert carrier) gases.

[0020] Generally, in an ALD cycle, during each cycle, a precursor is introduced into the reaction chamber and chemisorbs onto the deposition surface (e.g., a substrate surface, which may include previously deposited material or other materials from a previous ALD cycle) to form a monolayer or submonolayer of material that does not readily react with another precursor (i.e., a self-limiting reaction). A reactant (e.g., another precursor or a reactant gas) can then be introduced into the process chamber for use in converting the chemisorbed precursor to a desired material on the deposition surface. The reactant can further react with the precursor. A purge step is utilized during one or more cycles, e.g., during each step of each cycle, to remove excess precursor from the process chamber and / or to remove excess reactants and / or reaction by-products from the reaction chamber.

[0021] It should be noted that many example materials may be provided throughout the embodiments of the present disclosure, and the chemical formulas provided for each of the example materials should not be construed as limiting, nor should the non-limiting example materials provided be limited by certain example stoichiometries.

[0022] One object of the present disclosure is to provide a patterning device and method that avoids potential adhesion problems between photolithographic resists and underlying layers.

[0023] Another object of the present disclosure is to provide a patterning device and method that avoids photoacid dissociation to the resist / air interface.

[0024] Another object of the present disclosure is to provide a patterning device and method that enables a lithography procedure that is substantially free from scum defects and / or resist breaks.

[0025] Another object of the present disclosure is to provide a patterning device and method that enables a lithography procedure that is substantially immune to pattern collapse.

[0026] Another object of the present disclosure is to provide a patterning device and method that allows deposition of lithographic layers with high etch budgets.

[0027] 1 illustrates an exemplary substrate processing method according to at least one embodiment. Embodiments can include a substrate processing method for creating a sacrificial masking layer.

[0028] The substrate processing method 30 may include, for example, providing a substrate to a modifiable layer deposition apparatus in step 32, depositing a radiation-modifiable layer on the substrate in the modifiable layer deposition apparatus in step 34, and transferring the substrate with the radiation-modifiable layer to a lithographic projection apparatus for localized modification, for example patterning, in step 36. The substrate with the modifiable layer may also be obtained from elsewhere.

[0029] In fact, the modifiable layer may also be the top surface or a layer provided as the top surface of the substrate. The high energy radiation of EUV can change the properties of the top surface, which can shape the selectivity of the selective deposition process for making the etch mask.

[0030] In some embodiments, the modifiable layer may include carbon-containing chemical bonds selected from the list consisting of C-C, C-N, and C-O bonds. Such bonds may be suitably broken by EUV radiation, thereby locally modifying the properties of the modifiable layer in exposed areas. Such localized modifications may then be utilized for area-selective deposition.

[0031] In some embodiments, the radiation modifiable layer comprises one or more elements selected from the list consisting of Sn, Sb, Hf, In, and Te. Alternatively or additionally, the elements selected from the list consisting of Sn, Sb, Hf, In, and Te may be provided in an underlayer on which the radiation modifiable layer is deposited. Thus, in some embodiments, the process of depositing the radiation modifiable layer comprises depositing the radiation modifiable layer on an underlayer comprising an element selected from the list consisting of Sn, Sb, Hf, In, and Te. The underlayer may comprise, for example, SiOC and / or SiOCN, and may be deposited by known methods, for example, using PECVD or PEALD. Without the invention being bound to any theory or to a particular mode of operation, it is believed that these elements improve the sensitivity of the modifiable layer to EUV radiation through a relatively high capture cross-section of EUV photons.

[0032] In the lithographic projection apparatus, in step 38, the radiation-modifiable layer of the substrate can be patterned with exposure radiation of the lithographic projection apparatus to modify the radiation-modifiable layer exposed to the radiation. The substrate can then be moved from the lithographic projection apparatus to a reaction chamber of the selective deposition apparatus in step 40. In step 42, in the selective deposition apparatus, a first precursor selected to react with one of the modified layer portion and the unmodified layer portion and not react with the other of the modified layer portion and the unmodified layer portion can be provided in the reaction chamber to create a sacrificial masking layer.

[0033] Because the first precursor reacts only with one of the modified layer portion and the unmodified layer portion, and not with the other of the modified layer portion and the unmodified layer portion, the sacrificial masking layer can be made with an etch resistance that can be independent of the thickness of the radiation-modifiable layer. The radiation-modifiable layer provided in step 34 can have a thickness of one monolayer. The radiation-modifiable layer may have a thickness of two or more monolayers. The radiation-modifiable layer can have a thickness of 0.1 to 50 nm, or a thickness of 0.5 to 40 nm, more preferably a thickness of 5 to 20 nm. In some embodiments, the radiation-modifiable layer can have a thickness of at least 0.1 nm to a maximum of 0.5 nm, or at least 0.5 nm to a maximum of 1.0 nm, or at least 1.0 nm to a maximum of 2.0 nm, or at least 2.0 nm to a maximum of 5.0 nm, or at least 5.0 nm to 10.0 nm, or at least 10.0 nm to a maximum of 20.0 nm, or at least 20.0 nm to a maximum of 50.0 nm.

[0034] According to the present disclosure, it may not be necessary to remove parts of the radiation-modifiable layer with a special developer immediately after patterning with the exposure radiation of a lithographic projection apparatus. At very small feature sizes there may be a risk of pattern collapse after removing parts of the radiation-modifiable layer. With thicker radiation-modifiable layers the risk of pattern collapse may increase. By not removing parts of the radiation-modifiable layer with a developer, the radiation-modifiable layer can be more stabilized.

[0035] The first precursor can be selected to react with one of the modified layer portion and the unmodified layer portion and not react with the other of the modified layer portion and the unmodified layer portion. The etching resistance can be changed by the reaction of the first precursor with one of the modified layer portion and the unmodified layer portion, thereby creating a sacrificial masking layer. The substrate can be etched through the sacrificial masking layer, thereby removing one of the modified layer portion and the unmodified layer portion. After etching, the sacrificial masking layer is completely removed if it is no longer needed.

[0036] Thus, in some embodiments of the present disclosure, the radiation-modifiable layer can be used to form a plurality of recesses in the substrate. In such embodiments, the sacrificial masking layer may be suitably deposited on any one of the radiation-modifiable layer portions and the unmodified layer portions. The sacrificial masking layer may be deposited by, for example, plasma-enhanced atomic layer deposition (ALD), thermal ALD, radical-enhanced ALD (RETD), plasma-enhanced chemical vapor deposition (CVD), or thermal CVD.

[0037] In some embodiments, the sacrificial masking layer comprises a CH x The deposition is performed by a selective ALD process using a precursor that is more reactive towards OH groups compared to OH groups. Advantageously, the precursor used in such an embodiment is CH x The ALD process is substantially unreactive towards OH groups, and is more reactive towards OH groups. An example of a process using a precursor that may be more reactive towards OH groups than CH groups includes ALD of TiN or TiO2 using TiCl4 and NH3 or H2O TDMAT (tetrakis(dimethylamido)titanium) and H2O, and / or TTIP (titanium tetraisopropoxide) and H2O. Another example of a process using a precursor that may be more reactive towards OH groups includes ALD of Ru with EBECHRu (ethylbenzeneethyl-1,4-cyclohexadiene ruthenium). Without limiting the invention to a particular theory or mode of operation, it is believed that these processes exhibit delayed nucleation on CH3-terminated surfaces relative to OH-terminated surfaces, which can be exploited to provide selective growth on CH3-terminated surfaces and OH-terminated surfaces.

[0038] In some embodiments, the sacrificial masking layer comprises a CH x The precursors are deposited by a selective ALD process using precursors that are less reactive towards OH groups compared to OH groups. Advantageously, the precursors used in such embodiments are CH xThe process is highly reactive towards CH groups, which are less reactive or non-reactive towards OH groups. x The sacrificial masking layer can be selectively deposited on the OH-terminated surface and on the OH-terminated surface. For example, the precursor can include ruthenium tetroxide and H2 can be used as a reagent. Thus, the ruthenium-containing sacrificial masking layer can be deposited, for example, by thermal ALD or plasma-enhanced ALD using CH x It can be selectively deposited on the OH-terminated surface and on the OH-terminated surface.

[0039] After the sacrificial masking layer has been deposited, the substrate may be subjected to an etching step. Suitable such etching steps are known in the art. The sacrificial masking layer can be removed after the etching step, if desired, using techniques known per se.

[0040] If desired, the sacrificial masking layer deposition step and the etching step may be performed in one and the same reaction chamber. If desired, the optional sacrificial masking layer removal step can also be performed in the same reaction chamber.

[0041] A non-limiting example of a substrate processing apparatus of the present disclosure is illustrated in Figure 2, which includes a schematic diagram of an exemplary substrate processing apparatus 1 according to an embodiment of the present disclosure. It should be noted that the substrate processing apparatus 1 illustrated in Figure 2 is a simplified schematic diagram of an exemplary substrate processing apparatus and does not include every element, i.e., all valves, gas lines, heating elements, reactor components, etc., that may be utilized in the manufacture of a substrate processing apparatus of the present disclosure.

[0042] The exemplary substrate processing apparatus 1 can include a cassette-handling section 2 on which a cassette 3 having a plurality of substrates 15 can be placed. The cassette-handling section 2 can function as a fab input / output port for transporting substrates 15 between the substrate processing apparatus and the remainder of the fab in the cassette 3. The substrate processing apparatus 1 can be suitable for the substrate processing method of FIG.

[0043] The substrate processing apparatus may have a litho input / output port 5. The substrate may be transferred via the litho input / output port 5 to a lithographic projection apparatus.

[0044] The substrate processing apparatus may comprise a processing portion 4. In the processing portion 4, a modifiable layer deposition device 7 may be provided for depositing a radiation-modifiable layer on the substrate.

[0045] The modifiable layer deposition apparatus 7 may comprise a radiation modifiable coating apparatus for coating a radiation modifiable material (e.g., resist) on a substrate. The modifiable layer deposition apparatus 7 may comprise a rotatable substrate table 17 for rotating the substrate, and a liquid dispenser for supplying liquid to a surface of the substrate. The liquid radiation modifiable material (e.g., resist) may be supplied to the substrate while the substrate is rotated at 10-100 revolutions per second for 20-60 seconds.

[0046] In the processing section 4 a substrate handler 6 may be provided which transports substrates between the cassettes 3 in the cassette handling section 2, the modifiable layer deposition device 7 and the litho input / output port 5. The substrate handler 6 may have a horizontally and vertically movable substrate holder for this purpose.

[0047] In the processing section 4, a selective deposition apparatus 11 may be provided, which is provided with a reaction chamber 12 and a substrate table 13 for holding a substrate in the reaction chamber 12. To create a masking layer, a first precursor selected to react with one of the radiation modified layer portion and the unmodified layer portion and not react with the other of the radiation modified layer portion and the unmodified layer portion may be provided in the reaction chamber. The selective deposition apparatus may include a precursor distribution and removal system 14 including one or more reaction chamber valves for providing the gaseous first precursor to the reaction chamber 12 and removing it from the reaction chamber 12. A substrate handler 6 may be configured and arranged to move substrates to and from the selective deposition apparatus 11.

[0048] The substrate processing apparatus 1 may be provided with a control system 8 operatively connected to the substrate handler 6, the radiation-modifiable layer deposition device 7 and the selective deposition device 11, and may be provided with a memory M comprising a program. When a program in the memory M is executed by the control system 8, it: controlling the substrate handler 6 to pick up the substrate 15 from the cassette 3 at the cassette handling section 2, move the substrate to the modifiable layer deposition device 7 and place it on the rotatable substrate table 17; controlling a radiation-modifiable layer deposition apparatus 7 to deposit a radiation-modifiable layer on a substrate on a rotatable substrate table 17; The substrate handler 6 can be controlled to pick up the substrate from the rotatable substrate table 17 and move the substrate via the lithographic input / output port 5 to the lithographic projection apparatus, e.g. via the first and second substrate tables 16 of the lithographic input / output port 5. After locally modifying the radiation-modifiable layer with exposure radiation in the lithographic projection apparatus, the substrate can be returned to the substrate processing apparatus via the lithographic input / output port 5.

[0049] Execute the program in memory M of controller 8, picking up the substrate via the lithography input / output port 5 and controlling the substrate handler 6 to move the substrate to the selective deposition device 11; controlling a selective deposition apparatus 11 to supply a first precursor selected to react with one of the radiation-modified layer portion and the unmodified layer portion and not react with the other of the modified layer portion and the unmodified layer portion in a reaction chamber comprising a precursor delivery and removal system 14 for producing a sacrificial masking layer; The substrate handler 6 can be controlled to pick up the substrate from the selective deposition device 11 and move the substrate to the fab input / output port 2 .

[0050] A heating station 9 and a cooling station 10 may be provided in the processing section 4 for baking and cooling the substrate, respectively. The heating station 9 and the cooling station 10 may be supplied with substrates by a substrate handler 6. Heating and / or cooling may be required before the substrate is transported to a lithographic projection apparatus.

[0051] For example, the modifiable layer deposition apparatus may be omitted if the substrate having the radiation-modifiable layer 7 is obtained from elsewhere. In such a case, the substrate handler does not need to move the substrate to and from the modifiable layer deposition apparatus, but rather the substrate can be moved to the lithographic projection apparatus via the lithography input / output port.

[0052] Figure 3 illustrates a non-limiting selective deposition apparatus 11 for the substrate processing apparatus 1 of Figure 2. The selective deposition apparatus 11 may include a reaction chamber 12 constructed and arranged to hold at least a substrate 15 having a radiation-modifiable layer 106 thereon.

[0053] Reaction chambers 12 that can be used to selectively deposit the (first) precursor can include reaction chambers configured for atomic layer deposition (ALD) processes, or plasma-enhanced atomic layer deposition (PEALD), or radical-enhanced atomic layer deposition (REALD), as well as reaction chambers configured for chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), or metal organic CVD (MOCVD) processes. Reaction chambers 12 can also be either designed for plasma etching capabilities, capable of in-situ directional plasma etching, or can be coupled to reaction chamber 12b. According to some embodiments, showerhead reaction chambers can be used. According to some embodiments, cross-flow, batch, mini-batch, immersion or spatial ALD reaction chambers can be used.

[0054] In some embodiments of the present disclosure, a batch reaction chamber can be used. In some embodiments, a vertical batch reaction chamber can be used. In other embodiments, the batch reaction chamber comprises a mini-batch reactor configured to accommodate 10 or less wafers, 8 or less wafers, 6 or less wafers, 4 or less wafers, or 2 or less wafers.

[0055] A substrate holder 13 having at least one substrate 15 having a radiation-modifiable layer 106 disposed thereon, i.e., on the top surface of the substrate 15, can be disposed within the reaction chamber 12. In some embodiments of the present disclosure, the substrate 15 can comprise a planar substrate or a patterned substrate.

[0056] In some embodiments, the formation of the radiation-modifiable layer may be achieved by depositing an underlayer on the substrate, e.g., amorphous carbon (sp 3 / sp 2 The method includes depositing an amorphous carbon (carbon) underlayer. The amorphous carbon underlayer may be deposited, for example, by a hydrocarbon-containing precursor and plasma, such as a noble gas plasma, for example a helium plasma or an argon plasma. The radiation-modifiable layer may be formed on the surface of the underlayer by another plasma treatment. In some embodiments, the radiation-modifiable layer may include surface functional groups, such as NH2, Cl, F, and CH3 functional groups, on the amorphous carbon underlayer. In an exemplary embodiment, such groups may be formed on the surface of the amorphous carbon underlayer by subjecting the underlayer to a plasma treatment using a plasma containing F, Cl, N, and / or H. The NH2, Cl, F, and / or CH3 functional groups thus formed may be damaged upon exposure to extreme ultraviolet (EUV) radiation by cleavage of C-NH2, C-Cl, CF, and / or C-CH3 bonds, and may be replaced by C-OH groups when the wafer is exposed to oxygen. The oxygen can be provided, for example, by exposure within the reactor chamber or by exposing the substrate to atmospheric air.

[0057] (i) In some embodiments, the formation of the radiation-modifiable 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-modifiable layer. Exemplary functional groups that can be removed by EUV radiation include NH2, Cl, F, I, Br, and CH3. Removing one or more of these functional groups can dramatically change the surface properties of the exposed areas of the SAM-coated substrate. In some embodiments, the SAM can be deposited by CVD in an immersion mode, i.e., by exposing the substrate to the SAM vapor until SAM adsorption on the substrate reaches saturation. Alternatively, the SAM may be deposited by multiple SAM precursor pulses. This may improve densification of the SAM layer. The pulses may last, for example, 0.1-1.0 seconds, or 1.0-2.0 seconds, or 2.0-5.0 seconds, or 5.0-10.0 seconds, or 10.0-20.0 seconds.

[0058] In some embodiments, the radiation-modifiable layer comprises a polymer film. Such polymer films can be deposited, for example, by molecular layer deposition. Suitable films include polyimide, polyamide, and polyurea films. Exemplary polymer films may be deposited by the methods disclosed in U.S. Patent No. US10343186B2, the entirety of which is incorporated herein by reference.

[0059] 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 semiconductor materials such as gallium arsenide (GaAs), gallium phosphide (GaP), or gallium nitride (GaN). In some embodiments of the present disclosure, the substrate 15 comprises an engineered substrate having a surface semiconductor layer disposed on a bulk support with an intervening buried oxide (BOX) disposed therebetween.

[0060] The patterned substrate may comprise a substrate that may include semiconductor device structures formed in or on a surface of the substrate, for example, the patterned substrate may include partially fabricated semiconductor device structures, such as transistors and / or memory elements. In some embodiments, the substrate may include one or more secondary surfaces that may include a single crystal surface and / or a non-single crystal surface, such as a polycrystalline surface and / or an amorphous surface. The single crystal surface may include, for example, one or more of silicon (Si), silicon germanium (SiGe), germanium tin (GeSn), or germanium (Ge). The polycrystalline or amorphous surface may include a dielectric material, such as an oxide, oxynitride, or nitride, such as silicon oxide and silicon nitride.

[0061] In some embodiments of the present disclosure, the substrate 15 has a radiation-modifiable layer 106 disposed thereon, i.e., disposed on the top surface of the substrate 15. The radiation-modifiable layer 106 can include any material that can selectively react with the (first) precursor upon exposure to radiation to selectively grow a masking layer on the radiation-modifiable layer 106.

[0062] In some embodiments of the present disclosure, the radiation modifiable layer 106 can include at least one of a polymer resist, such as a photoresist, an extreme ultraviolet (EUV) resist, an immersion photoresist, a chemically amplified resist (CAR), or an electron beam resist (e.g., poly(methyl methacrylate) (PMMA)). The radiation modifiable layer 106 can also be a metal, an oxide, a self-assembled monolayer (SAM), or any other material. Additionally or alternatively, the radiation modifiable layer 106 can include C, N, H, and / or O. Optionally, the radiation modifiable layer includes C—F bonds, C—Cl bonds, and / or C—NH2 bonds. These bonds can be broken by irradiation with EUV photons, which can locally change the properties of the layer and affect the dry and / or wet etch rates. Additionally or alternatively, it can enable selective deposition on exposed and unexposed areas, such as area-selective sacrificial masking layer deposition.

[0063] In some embodiments, the radiation modifiable layer further comprises one or more elements selected from the list consisting of Sn, Sb, Hf, In, and Te. Alternatively or additionally, the elements selected from the list consisting of Sn, Sb, Hf, In, and Te may be provided in an underlayer on which the radiation modifiable layer is deposited. Thus, in some embodiments, the process of depositing the radiation modifiable layer comprises depositing the radiation modifiable layer on an underlayer comprising an element selected from the list consisting of Sn, Sb, Hf, In, and Te. Without the invention being bound to any theory or to a particular mode of operation, it is believed that these elements may improve the sensitivity of the modifiable layer to EUV radiation through a relatively high capture cross-section of EUV photons.

[0064] In some embodiments of the present disclosure, the radiation-modifiable layer 106 can include porous materials, such as microporous and / or nanoporous materials, including, for example, spin-on-glass (SOG), and spin-on-carbon (SOC). In some embodiments of the present disclosure, the radiation-modifiable layer 106 can comprise one or more sacrificial masking layer materials, including, but not limited to, boron carbide, amorphous carbon, silicon oxide, silicon nitride, and silicon oxynitride.

[0065] In some embodiments of the present disclosure, the radiation-modifiable layer 106 can comprise a patterned radiation-modifiable material, such as a patterned resist or a patterned sacrificial masking layer comprising one or more features. The features can be transferred to the underlying substrate during a subsequent etching process. The features can include any shape that can be formed in response to an exposure and associated development process, including, but not limited to, line features, block features, open-hole features, and circular features.

[0066] In some embodiments of the present disclosure, the radiation-modifiable layer 106 can comprise a planar radiation-modifiable material that can be patterned during subsequent processing after localized modification. For example, the radiation-modifiable layer 106 can comprise a planar resist, or the radiation-modifiable layer 106 can be patterned during a subsequent lithographic exposure step.

[0067] The substrate 15 may be disposed within the reaction chamber 12 and held in place by a substrate holder 13 configured to hold at least one substrate thereon. In some embodiments of the present disclosure, the selective deposition processes disclosed herein may utilize a process to heat the substrate 15 and associated radiation-modifiable layer 106 to a suitable process temperature. Accordingly, the substrate holder 13 may include one or more heating elements 110 that may be configured to heat the substrate 15 with the radiation-modifiable layer 106 disposed thereon.

[0068] 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., such as to 85° C. In some embodiments of the present 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, preferably between 0.1 and 500, and most preferably between 1 and 100 Torr.

[0069] In some embodiments of the present disclosure, the selective deposition apparatus 11 can include a precursor distribution and removal system 14. The precursor distribution and removal system can include a gas supply system 112 that can further include one or more precursor sources 114A and 114B configured and arranged to provide a vapor of some precursor and distribute the associated vapor to the reaction chamber 12. The gas supply system 112 can also include a source container 116 configured to store and distribute a purge gas that can be utilized in a purge cycle of the exemplary selective deposition process described herein. The gas supply system 112 can also include a reactant source container 118 configured to contain and distribute a precursor to the reaction chamber 12 as utilized in the exemplary selective deposition process described herein. As a non-limiting example, the selective deposition apparatus 11 can include a first precursor source 114A configured and arranged to provide a vapor of a first precursor. In some embodiments, the first precursor source 114A can include a first precursor vaporizer configured and arranged to vaporize the first precursor.

[0070] In some embodiments, the first precursor source 114A can comprise a source container configured to store and contain the first precursor under suitable operating conditions. For example, the first precursor can include a solid precursor, a liquid precursor, or a gas phase precursor, and the source container can be configured to store and contain the solid, liquid, or gas phase precursor under suitable operating conditions.

[0071] In some embodiments, the first precursor source can comprise a first precursor vaporizer, which can comprise one or more controllable heating elements, capable of heating the first precursor to a suitable operating temperature, thereby controllably vaporizing a portion of the first precursor, which is then distributed to the reaction chamber 12 by suitable means for selective deposition onto the radiation-modifiable layer. In some embodiments, the one or more heating elements associated with the first precursor source 114A can be configured to control the vapor pressure of the first precursor. Additionally, a flow controller 120A, e.g., a mass flow controller (MFC), can be further associated with the first precursor source 114A and configured to control the mass flow rate of vapor generated from the first precursor source 114A, e.g., the first precursor vaporizer. In addition to the flow controller 120A, a valve 122A, e.g., a shutoff valve, can be associated with the first precursor source 114A and can be utilized to isolate the first precursor source 114A from the reaction chamber 12. That is, when the valve 122A is in the closed position, vapor generated by the first precursor source 114A is prevented from entering the reaction chamber 12.

[0072] In further embodiments, the first precursor source 114A may further comprise a carrier gas input device (not shown) such that a carrier gas (e.g., nitrogen) may be passed over or bubbled through the first precursor such that the first precursor may be entrained in the carrier gas, and the carrier gas / first precursor vapor may then be delivered to the reaction chamber 12 by suitable means.

[0073] In some embodiments of the present disclosure, the selective deposition apparatus 11 ( FIG. 3 ) can include a precursor distribution and removal system 14 configured and arranged to supply vapor of a first precursor from a first precursor source 114A to the reaction chamber 12 and to remove vapor of the first precursor from the reaction chamber 12.

[0074] In some embodiments of the present disclosure, the selective deposition apparatus 11 can include a precursor delivery and removal system 14 configured and arranged to supply a vapor of a first precursor from a first precursor source 114A comprising an element, e.g., a metal or a semiconductor, e.g., a Group IV semiconductor, to the reaction chamber 12. The element, e.g., a metal or a semiconductor, in the reaction chamber 12 can be selected from the group including 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).

[0075] In some embodiments of the present disclosure, the selective deposition apparatus 11 can include a precursor delivery and removal system 14 constructed and arranged to deliver precursors including alkylamide precursors, such as metal alkylamide precursors or Group IV semiconductor alkylamide precursors, into the reaction chamber 12.

[0076] In some embodiments of the present disclosure, the selective deposition apparatus 11 can include a precursor delivery and removal system 14 configured and arranged to deliver a precursor selected from the group including trimethylaluminum (TMA), triethylaluminum (TEA), and dimethylaluminum hydride (DMAH), such that the selective deposition apparatus can selectively deliver a metal, such as aluminum, to or onto one of a modified or unmodified layer portion, such as a resist.

[0077] In some embodiments of the present disclosure, the selective deposition apparatus 11 can include a precursor delivery and removal system 14 configured and arranged to supply a vapor of a first precursor from a first precursor source 114 to the reaction chamber 12, which can include a metal halide or a halide of a Group IV semiconductor within the reaction chamber 12.

[0078] In some embodiments of the present disclosure, the precursor delivery and removal system 14 of the selective deposition apparatus 11 is configured and arranged to deliver a precursor including SnI4 or SnCl4 into the reaction chamber. In some embodiments of the present disclosure, the exemplary selective deposition apparatus 11 can include a precursor delivery and removal system configured and arranged to deliver a precursor selected from a group including tetraethyltin, tetramethyltin, or acetylacetonate tin into the reaction chamber. The selective deposition apparatus 11 can thereby selectively deliver a metal, such as tin, to or onto one of modified or unmodified layer portions of a layer such as a resist.

[0079] In some embodiments of the present disclosure, the exemplary selective deposition apparatus 11 can include a precursor delivery and removal system 14 configured and arranged to supply a vapor of a first precursor from a first precursor source 114 to the reaction chamber 12, which can include a metal or Group IV semiconductor, e.g., magnesium and / or calcium, in the reaction chamber.

[0080] In some embodiments, the selective deposition apparatus 11 may be constructed and arranged to selectively deposit silicon on or onto one of modified and unmodified layer portions, such as, for example, resist.

[0081] In some embodiments, the first precursor source 114A may be constructed and arranged to provide a vapor of an aminosilane.

[0082] More specifically, the precursor distribution system can include a gas supply 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 vessel 116, and a gas line 130 in fluid communication with a reactant source vessel 118. As a non-limiting example, the gas line 124 can be in fluid communication with the first precursor source 114A and configured to supply vapor of the first precursor to the reaction chamber 12.

[0083] The precursor distribution system may further include a gas dispenser 132 configured to distribute vapor of the first precursor into the reactive chamber 12 and onto the substrate 15 having the radiation-modifiable layer 106 disposed thereon, the gas dispenser 132 being in fluid communication with the gas lines 126, 128, and 130 as well as in fluid communication with the gas line 124.

[0084] As a non-limiting exemplary embodiment, the gas dispenser 132 can comprise a showerhead, as illustrated in block form in FIG. 3. Although the showerhead is illustrated in block form, it should be noted that the showerhead can be a relatively complex structure. In another embodiment, the showerhead can be configured to maintain separation between the vapors introduced to the showerhead, and the vapors contact each other only near the substrate 15 disposed within the reaction chamber 12. Furthermore, the showerhead can be configured to provide vertical or horizontal gas flow into the reaction chamber 12. An exemplary gas distributor is described in U.S. Pat. No. 8,152,922, the contents of which are incorporated herein by reference to the extent not inconsistent with the present disclosure.

[0085] As illustrated in FIG. 3, the precursor distribution system can include a gas supply system 112, at least gas lines 124, 126, 128, and 130, and a gas distributor 132, although it should be noted that the precursor distribution system can include other components not illustrated in FIG. 3, such as other gas lines, valves, actuators, seals, and heating elements.

[0086] In addition to the precursor delivery system, the precursor delivery and removal system 14 of the selective deposition apparatus 11 can also include a removal system configured and arranged to remove gases from the reaction chamber 12. In some embodiments, the removal system can include an exhaust port 134 disposed in a 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 gases from within the reaction chamber 12. Once the gas(es) are exhausted from the reaction chamber 12 utilizing the vacuum pump 138, they can be conveyed along another exhaust line 140 to exit another station 11 where they can undergo further abatement processes.

[0087] To further aid in the removal of precursor gas, i.e., reactive vapor, from within the reaction chamber 12, the removal system may further comprise a source container 116 in fluid communication with the gas distributor 132 via a gas line 128. For example, the source container 116 may be configured to contain and store a purge gas, such as argon (Ar), nitrogen (N2), or helium (He). A flow controller 120C and a valve 122C associated with the source container 116 may control the flow rate, particularly the mass flow rate, of the purge gas provided through the gas line 128 to the gas distributor 132 and into the reaction chamber 12. The purge gas may aid in the removal of vapor-phase precursor gas, inert gas, and by-products from within the reaction chamber 12, and in particular, may remove precursor gas and unreacted by-products from the exposed surface of the modifiable layer 106. The purge gas (and any associated precursors and by-products) may exit the reaction chamber 12 via an exhaust port 134 utilizing a vacuum pump 138.

[0088] In some embodiments of the present disclosure, the selective deposition apparatus 11 may further comprise a sequence controller operably connected to the precursor delivery system and the removal system and comprising a memory 144 comprising a program that, when executed on the sequence controller 142, performs selective deposition on or at one of the radiation-modified layer and the unmodified layer. Sequence Controller

[0089] More specifically, the exemplary selective deposition apparatus 11 can include a sequence controller 142, which can also include control lines 144A, 144B, and 144C, which can couple various systems and / or components of the selective deposition apparatus 11 to the sequence controller 142. For example, the control line 144A can couple the sequence controller 142 to the gas supply system 112, thereby controlling the gas lines 124, 126, 128, and 130, as well as the precursor distribution system, including the gas distributor 132. The control line 144B can couple the sequence controller 142 to the reaction chamber 12, thereby controlling the operation of the reaction chamber, including, but not limited to, the process pressure and the substrate table 13 temperature. The control line 144C can couple the sequence controller 142 to the vacuum pump 138, such that operation and control of the gas removal system can be provided by the sequence controller 142. The sequence controller 142 can be operatively connected to the control system 8 (FIG. 2).

[0090] As illustrated in FIG. 3, the sequence controller 142 has three control lines 144A, 144B, and 144C, however, multiple control lines, i.e., electrically and / or optically connected control lines, may be utilized to couple any desired system and component comprising the selective deposition apparatus 11 to the sequence controller 142, thereby controlling the entire apparatus.

[0091] In some embodiments of the present disclosure, the sequence controller 142 can include electronic circuitry for selectively operating valves, heaters, flow controllers, manifolds, pumps, and other equipment included in the exemplary selective deposition apparatus 11. Such circuits and components operate to introduce precursor and purge gases from the respective precursor sources 114A, 114B, reactant source vessel 118, and purge gas source vessel 116. The sequence controller 142 can also control the timing of the precursor pulse sequences, the temperature of the substrate and reaction chamber 12, and the pressure of the reaction chamber, as well as various other operations necessary for the proper operation of the selective deposition apparatus 11. In some embodiments, the sequence controller 142 can also include control software and electrically or pneumatically controlled valves for controlling the flow rates of precursor and purge gases into and out of the reaction chamber 12. In some embodiments of the present disclosure, the sequence controller 142 can include a memory 144 that includes a program that, when executed on the sequence controller, performs selective deposition on or at the radiation-modifiable layer. For example, the sequence controller 142 can include modules, such as software or hardware components, such as FPGAs or ASICs, that perform particular selective deposition processes. The modules can be configured to reside on an addressable storage medium of the sequence controller 142 and can be configured to perform one or more selective deposition processes.

[0092] In some embodiments of the present disclosure, the memory 144 of the sequence controller 142 may include a program for providing a precursor selected to react with one of the modified layer portion and the unmodified layer portion in the reaction chamber and not react with the other of the modified layer portion and the unmodified layer portion, and activating the precursor distribution system and removal system to provide vapor of the precursor to the radiation-modifiable layer 106 on the substrate 15 in the reaction chamber 12, whereby the precursor selectively reacts with one of the modified layer portion and the unmodified layer portion of the radiation-modifiable layer 106 on the substrate 15, thereby creating a sacrificial masking layer.

[0093] In some embodiments of the present disclosure, the exemplary selective deposition apparatus 11 can include a second precursor source 114B, such as a second precursor evaporator. More specifically, the second precursor source 114B can be constructed and arranged to provide a vapor of a second precursor. For example, the second precursor source 114B can include a second precursor evaporator that can be constructed and arranged to evaporate a second precursor. In some embodiments, the second precursor source 114B can be the same or substantially the same as the first precursor source 114A, and thus details regarding the second precursor source 114B are omitted for brevity.

[0094] In some embodiments, the precursor delivery and removal system 14 may be configured and arranged to supply a vapor of a second precursor from a second precursor source 114B to the reaction chamber 12. For example, the gas line 126 may be in fluid communication with the second precursor source 114B via a flow controller 120B and a valve 122B to supply a vapor of the second precursor from the second precursor source 114B to the gas distributor 132 and subsequently into the reaction chamber 12. In some embodiments, a program in the memory 144, when executed on the sequence controller 142, may be programmed to perform selective deposition on or at the radiation-modifiable layer 106 by operating the precursor delivery and removal system to supply a vapor of the second precursor to the reaction chamber 12, whereby the second precursor reacts with one of the modified layer portion 106 and the unmodified layer portion in the reaction chamber and does not react with the other of the modified layer portion and the unmodified layer portion to create a sacrificial masking layer on the substrate 15.

[0095] In some embodiments of the present disclosure, the program in the memory 144, when executed on the sequence controller 142, can be programmed to operate the precursor delivery system and removal system to supply a first precursor followed by a second precursor, i.e., the first precursor source 114A can supply a vapor of the first precursor into the reaction chamber 12 to selectively deposit material on or at the radiation modifiable layer 106 with the first precursor, and subsequently the second precursor source 114B can supply a vapor of the second precursor into the reaction chamber 12 to selectively deposit the second precursor on or at the radiation modifiable layer 106, thereby performing selective deposition on the radiation modifiable layer 106. The selective deposition cycle of the program stored in the memory 144, when executed on the sequence controller 142, can have a first period of supplying a vapor of the first precursor that is longer than a third period of supplying a vapor of the second precursor to perform selective deposition on or at the radiation modifiable layer 106.

[0096] In some embodiments, the sequence controller 142 may execute a program on the memory 144 to operate the precursor delivery system and removal system to supply the first precursor after the second precursor. That is, the second precursor source 114B can supply 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 can supply vapor of the first precursor to the reaction chamber 12 for selective deposition on the modifiable layer 106.

[0097] In some embodiments of the present disclosure, a program stored in memory 144, when executed on the sequence controller 142, can be programmed to perform selective deposition on the radiation-modifiable layer 106 by operating the precursor delivery system and removal system to supply a first precursor to the reaction chamber 12, followed by a purge cycle to remove excess first precursor and any by-products from the reaction chamber, and then supply a second precursor to the reaction chamber, followed by a second purge cycle to remove excess second precursor and any by-products from the reaction chamber.

[0098] More specifically, the program in the memory 144 of the sequence controller 142 can first activate the first precursor source 114A to supply vapor of the first precursor to the reaction chamber 12 for selective deposition on or at the radiation-modifiable layer 106, after which 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 released, for example, by the valve 122A associated with the first precursor source 114A. Upon deactivating and isolating the first precursor source 114A from the reaction chamber 12, the program stored in the memory 144 of the sequence controller 142 can engage or continue to engage the vacuum pump 138 to evacuate excess vapor of the first precursor and any by-products from the reaction chamber 12. In a further embodiment, in addition to utilizing the vacuum pump 138 to evacuate excess vapor of the first precursor and any by-products from the reaction chamber 12, the program stored in the memory 144 of the sequence controller 142 can activate the source vessel 116 containing a source of purge gas, for example by opening the valve 122C associated with the source vessel 116. The purge gas can flow through the gas line 128 via the gas distributor 132 into the reaction chamber 12 to purge the reaction chamber 12, and in particular 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 supplying vapor of the second precursor to the reaction chamber 12 and in particular selectively depositing the second precursor vapor supplied by the second vapor source 114B on the radiation-modifiable layer 106. The program stored in the memory 144 of the sequence controller 142 can then stop the flow of vapor of the second precursor into the reaction chamber 12 and then activate the source container 116 to purge the reaction chamber again, e.g., to remove excess vapor of the second precursor.

[0099] In some embodiments of the present disclosure, a program stored in memory 144, when executed on the sequence controller 142, can be programmed to perform selective deposition on or at the radiation-modifiable layer 106 by operating the precursor delivery system and removal system to supply vapor of a second precursor to the reaction chamber, followed by a purge cycle to remove excess vapor of the second precursor and any by-products from the reaction chamber, and then supply vapor of a first precursor to the reaction chamber, followed by a purge cycle to remove excess vapor of the first precursor and any by-products from the reaction chamber.

[0100] In further embodiments of the present disclosure, in addition to the first precursor source 114A and the second precursor source 114B, the exemplary alternative station 11 can further comprise a reactant source container 118 and a reactant supply line, i.e., a gas line 130, constructed and arranged to supply reactants including an oxygen precursor to the reaction chamber 12.

[0101] In some embodiments of the present disclosure, reactant source container 118 can contain reactants in solid, liquid, or gas phases. In some embodiments, reactant source container 118 can include a reactant vaporizer, i.e., one or more heating elements can be associated with the reactant source container to enable vaporization of the reactants, thereby providing vaporized reactants, including the oxygen precursor, to reaction chamber 12.

[0102] In some embodiments, control of the flow rate of the vapor reactant including the oxygen precursor to the reaction chamber can be achieved by using a valve 122D and a flow controller 120D, both associated with the reactant source container 118. In some embodiments of the present disclosure where the reactant source container 118 further comprises a reactant vaporizer, the reactant vaporizer can be constructed and arranged to vaporize at least one of water (H2O) or hydrogen peroxide (H2O2) as the reactant including the oxygen precursor.

[0103] In some embodiments of the present disclosure, reactant source container 118 can store and distribute a gaseous oxygen precursor to reaction chamber 12 via reactant supply line 130 and gas distributor 132. In some embodiments, the gaseous oxygen precursor can include at least one of ozone (O3) or molecular oxygen (O2).

[0104] In some embodiments of the present disclosure, the exemplary selective deposition apparatus 11 may optionally further include a plasma generator 146. The plasma generator 146 may be constructed and arranged to generate a plasma from a gaseous oxygen precursor, thereby providing one or more of atomic oxygen, oxygen ions, oxygen radicals, and excited species of oxygen to the reaction chamber 12, whereby the oxygen-based plasma generated by the plasma generator 146 may react with the layer 106 disposed on the substrate 15.

[0105] In some embodiments, each step of the programmed sequence may be followed by a purge cycle to remove excess precursors and by-products from the reaction chamber by evacuating the reaction chamber 12 using a vacuum pump 138 and, if necessary, flowing a purge gas from the source container 116. In some embodiments, the programmed sequence of supplying an oxygen precursor followed by supplying vapor of a first precursor may be repeated one or more times. In some embodiments, each step of the programmed sequence may be followed by a purge cycle to remove excess precursors and by-products from the reaction chamber by evacuating the reaction chamber 12 using a vacuum pump 138 and, if necessary, flowing a purge gas from the source container 116.

[0106] In some embodiments of the present disclosure, a program in memory 144, when executed on sequence controller 142, is programmed to perform selective deposition on or at layer 106 by operating the precursor delivery system and removal system to supply a first precursor, followed by a reactant, followed by a second precursor, and then a reactant.

[0107] In some embodiments, the program in the memory 144, when executing on the sequence controller 142, can be programmed to operate the precursor delivery and removal system 14 to perform selective deposition on or at the layer 106 by repeating multiple times to supply a first precursor, followed by a reactant, followed by a second precursor, and then a reactant.

[0108] In some embodiments, the program in memory 144, when executing on the sequence controller 142, can be programmed to perform selective deposition on or at layer 106 by operating the precursor delivery system and removal system to remove precursors and / or reactants from the reaction chamber between each step of delivering a first precursor, followed by a reactant, followed by a second precursor, and then by a reactant.

[0109] In some embodiments of the present disclosure, a program in memory 144, when executed on the sequence controller 142, can be programmed to operate the precursor delivery system and removal system to perform selective deposition on or at layer 106 by supplying a first precursor, followed by a second precursor, and followed by a reactant. In some embodiments, the program sequence of supplying a first precursor, followed by a second precursor, and followed by a reactant can be repeated one or more times. In some embodiments, each step of the program sequence can be followed by a purge cycle to evacuate the reaction chamber 12 utilizing the vacuum pump 138 and to remove excess precursors and by-products from the reaction chamber by flowing a purge gas from the source container 116 as needed.

[0110] In some embodiments of the present disclosure, a program in memory 144, when executed on the sequence controller 142, can be programmed to operate the precursor delivery system and removal system to perform selective deposition on or at layer 106 by supplying a second precursor, followed by a first precursor, and followed by a reactant. In some embodiments, the program sequence of supplying a second precursor, followed by a first precursor, and followed by a reactant can be repeated one or more times. In some embodiments, each step of the program sequence can be followed by a purge cycle to evacuate the reaction chamber 12 utilizing the vacuum pump 138 and to remove excess precursor and by-products from the reaction chamber by flowing a purge gas from the source container 116 as needed.

[0111] In some embodiments of the present disclosure, a program in memory 144, when executed on the sequence controller 142, can be programmed to operate the precursor delivery system and removal system to perform selective deposition on or at layer 106 by supplying a first precursor, followed by a reactant, and then a second precursor. In some embodiments, the program sequence of supplying a first precursor, followed by a reactant, and then a second precursor can be repeated one or more times. In some embodiments, each step of the program sequence can be followed by a purge cycle to evacuate the reaction chamber 12 utilizing the vacuum pump 138 and to remove excess precursors and by-products from the reaction chamber by flowing a purge gas from the source container 116 as needed.

[0112] In some embodiments of the present disclosure, a program in memory 144, when executed on the sequence controller 142, can be programmed to operate the precursor delivery and removal systems to perform selective deposition on or at layer 106 by supplying a reactant, followed by supplying a first precursor, followed by supplying a second precursor, followed by supplying a reactant. In some embodiments, the program sequence of supplying a reactant, followed by supplying a first precursor, followed by supplying a second precursor, followed by supplying a reactant, can be repeated one or more times. In some embodiments, each step of the program sequence can be followed by a purge cycle to evacuate the reaction chamber 12 utilizing the vacuum pump 138 and to remove excess precursors and by-products from the reaction chamber by flowing a purge gas from the source container 116 as needed.

[0113] In some embodiments of the present disclosure, a program in memory 144, when executed on the sequence controller 142, can be programmed to operate the precursor delivery and removal systems to perform selective deposition on or at layer 106 by supplying a reactant, followed by supplying a first precursor, followed by supplying a reactant, followed by supplying a second precursor. In some embodiments, the program sequence of supplying a reactant, followed by supplying a first precursor, followed by supplying a reactant, followed by supplying a second precursor can be repeated one or more times. In some embodiments, each step of the program sequence can be followed by a purge cycle to evacuate the reaction chamber 12 utilizing the vacuum pump 138 and to remove excess precursors and by-products from the reaction chamber by flowing a purge gas from the source container 116 as needed.

[0114] FIG. 4 illustrates a resistless patterning method according to one embodiment of the present disclosure. Panel 1) shows a radiation-modifiable layer (410) deposited on a substrate (430). As illustrated, an optional underlayer (420) can be provided between the substrate (430) and the radiation-modifiable layer (410). In some embodiments, the radiation-modifiable layer (410) can consist of a surface of the underlayer (420). Of course, in another embodiment, the radiation-modifiable layer (410) can be deposited directly on the substrate, thus not requiring an underlayer (420). Panel 2) shows how the radiation-modifiable layer (410) is exposed to extreme ultraviolet (EUV) radiation, thereby creating a plurality of radiation-modified layer portions (411) and a plurality of unmodified layer portions (412). A sacrificial masking layer can then be selectively deposited either on the radiation-modified layer portion (411) as shown in panel 3b) or on the unmodified layer portion (412) as shown in panel 3a). A subsequent etching step forms a recess (450) as shown in panels 4a and 4b. In particular, panel 4b shows how a recess (450) is etched under the unmodified layer portion (412) when a sacrificial masking layer (440) is deposited on the radiation-modified layer portion (411). Panel 4a shows how a recess (450) is etched under the radiation-modified layer portion (411) when a sacrificial masking layer (440) is deposited on the unmodified layer portion (412). If desired, the sacrificial masking layer deposition step and the etching step may be performed in one and the same reaction chamber. If desired, an optional sacrificial masking layer removal step can also be performed in the same reaction chamber.

[0115] Figure 5 illustrates a resistless patterning method according to one embodiment of the present disclosure. Panel 1) shows a radiation-modifiable layer (410) deposited on a substrate (430). The radiation-modifiable layer (410) may include organic compounds containing C, N, H, and / or O, and may be locally modified by photons, e.g., extreme ultraviolet (EUV) photons. This may result in a localized change in etch rate for a wet or dry etching process.

[0116] As illustrated, an optional underlayer (420) can be provided between the substrate (430) and the radiation-modifiable layer (410). In some embodiments, the radiation-modifiable layer (410) can consist of a surface of the underlayer (420). Of course, in another embodiment, the radiation-modifiable layer (410) can be deposited directly on the substrate, thus not requiring the underlayer (420). Panel 2) shows how the radiation-modifiable layer (410) is exposed to extreme ultraviolet (EUV) radiation, thereby creating a plurality of radiation-modified layer portions (411) and a plurality of unmodified layer portions (412). Panel 3) shows how the unmodified layer portions (412) are removed in the layer removal step, while the radiation-modified layer portions (411) remain in their original positions. In another embodiment (not shown), the unmodified layer portions remain in their original positions as they are not affected by the layer removal step, and the radiation-modified layer portions (411) are removed during the layer removal step.

[0117] After the etching step of panel 3), a sacrificial masking layer can be selectively deposited. The sacrificial masking layer may be deposited, for example, on the radiation-modified layer portions (411) as shown in panel 4a) or on the exposed underlayer as shown in panel 4b). If no underlayer is present, the sacrificial masking layer may be deposited directly on the substrate (430) (not shown in the embodiment). If the radiation-modified layer portions are removed and the unmodified layer portions remain in place during the layer removal step, the sacrificial masking layer can be deposited on the unmodified layer portions (not shown in the embodiment).

[0118] The deposition of a sacrificial masking layer is then followed by an etching step, which results in the formation of recesses (450) in the areas where the sacrificial masking layer is not deposited, as shown for example in panels 5a and 5b. In particular, panel 5a shows how recesses (450) are etched at the locations of the unmodified layer portions (412) if the sacrificial masking layer (440) is deposited on the radiation-modified layer portions (411). Panel 5b shows how recesses (450) are etched at the locations of the radiation-modified layer portions (411) if the sacrificial masking layer (440) is deposited on the unmodified layer portions (412). Of course, the same principle applies to the other embodiments: the areas where the sacrificial masking layer is not deposited are etched during the etching step, and the areas where the sacrificial masking layer is deposited are not etched or are substantially not etched during the etching step. If necessary, after the etching step the sacrificial masking layer can be removed. If necessary, the sacrificial masking layer deposition step and the etching step may be performed in one and the same reaction chamber. If desired, the optional sacrificial masking layer removal step can also be performed in the same reaction chamber.

[0119] A suitable radiation-modifiable layer (410) includes an amorphous carbon layer, for example an amorphous carbon layer deposited by plasma-enhanced atomic layer deposition (PEALD) or by plasma-enhanced chemical vapor deposition (PECVD). 2 and sp 3The amorphous carbon layer may include carbon. In other words, the amorphous carbon layer may include C-C, C=C, and C-H bonds. Additionally, the amorphous carbon may include C-N and / or C-O bonds. When an area of ​​the amorphous carbon layer is exposed to EUV light, the C=C, C-H, C-N, and C-O bonds may be broken. Without limiting the invention to any particular theory or mode of operation, it is believed that the resulting damage may allow the exposed amorphous carbon layer portion to be selectively etched by H radicals at low temperatures, e.g., at temperatures below 100°C, or below 90°C, or below 80°C, or below 70°C, or below 60°C, or below 50°C, or below 40°C. The 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 the H radicals at these low temperatures because the unexposed amorphous carbon layer portions are not damaged by the EUV exposure and because the C-C bonds of the amorphous carbon are not substantially etched by the H radicals. Furthermore, without limiting the invention to any particular theory or mode of operation, it is believed that the H radicals hydrogenate the surface of the amorphous carbon layer, thus resulting in the formation of CH3 end groups on the surface. Thus, it is believed that regions having amorphous carbon terminated with CH3 can thus be formed, which can be used as a blocking layer or an active layer during deposition of the sacrificial masking layer.

[0120] One example of a sacrificial masking layer that can be selectively deposited on CH3-terminated amorphous carbon is RuO2, starting, for example, with a precursor that includes RuO4 in an organic solvent. Compositions that include RuO4 in an organic solvent are commercially available.

[0121] An example of a masking layer that can be selectively deposited on the underlayer or substrate, but not on the CH3-terminated amorphous carbon, is TiO (i.e., titanium oxide). x , TiOx C y (i.e., titanium oxycarbide), or atomic layer deposition of TiN with titanium halide precursors, such as TiCl4, atomic layer deposition of hafnium oxide with hafnium halide precursors, such as HfCl4, and atomic layer deposition of ruthenium with EBECHRu. Underlayers and substrates on which these materials can be selectively deposited relative to CH3-terminated amorphous carbon include metal-based underlayers, silicon-based underlayers, and substrates, such as single crystal silicon, spin-on silicon, and low-k dielectrics. When the masking layer is selected from titanium oxide, titanium nitride, and ruthenium, a suitable underlayer for selective deposition relative to CH3-terminated amorphous carbon can include SiO2, SiN, and / or SiON. When the masking layer is selected from titanium oxide or titanium nitride, a suitable underlayer for selective deposition relative to CH3-terminated amorphous carbon can include ruthenium. And when ruthenium is used as a masking layer, a suitable underlayer for selective deposition to CH3-terminated amorphous carbon can include titanium oxide or titanium nitride. In some embodiments, the underlayer can further include tin, which can reduce the EUV dose required to achieve adequate exposure.

[0122] The method and device provide numerous advantages when used for deposition, etching, and / or other purposes. For example, it may avoid problems associated with resist collapse. Conversely, conventional techniques using thick resist lines (e.g., 30 nm thick) may suffer from resist line collapse during wet development steps if the adhesion between the resist and the underlayer is not strong enough. Furthermore, the method disclosed herein avoids problems that may arise when using resists that include photoacid generators (PAGs), such as PAG separation and PAG quenching. Furthermore, the method of the present invention requires only a very thin underlayer and allows for selective deposition of a sacrificial masking layer with excellent etch budget when used for etching purposes, even when very high resolution is provided, e.g., 13 nm resolution, or about 8 nm resolution if a high numerical aperture is used.

[0123] The exemplary embodiments of the present disclosure described above are merely examples of embodiments of the present invention, as defined by the appended claims and their legal equivalents, and therefore do not limit the scope of the present invention. Any equivalent embodiments are intended to be within the scope of the present invention. Indeed, various modifications of the present disclosure in addition to those shown and described herein may become apparent to those skilled in the art from the description, such as alternative useful combinations of the described elements. Such modifications and embodiments are also intended to fall within the scope of the appended claims. [Explanation of symbols]

[0124] 410 Radiation-modifiable layer 411 Radiation modified layer 412 Unmodified layer part 420 Base layer 430 Base material 440 Sacrificial Masking Layer 450 Recess

Claims

1. 1. A substrate processing apparatus for creating a sacrificial masking layer on a substrate, comprising: a lithography input / output port for transporting substrates between the substrate processing equipment and a lithographic projection apparatus; a selective deposition apparatus for providing into a reaction chamber a first precursor selected to react with one of the radiation-modified layer portion and the unmodified layer portion and not react with the other of the radiation-modified layer portion and the unmodified layer portion to create the sacrificial masking layer; a substrate handler for transporting substrates between the lithography input / output port and the selective deposition apparatus; a control system operatively coupled to the substrate handler and the selective deposition device, the control system comprising a memory comprising a program; When the program is executed by the control system, controlling the substrate handler to pick up a substrate via the lithography input / output port and move it to the selective deposition apparatus; controlling the selective deposition apparatus to deliver into the reaction chamber a first precursor selected to react with one of the radiation-modified layer portion and the unmodified layer portion and not react with the other of the radiation-modified layer portion and the unmodified layer portion to create the sacrificial masking layer; the substrate processing apparatus comprises a radiation-modifiable layer deposition apparatus for depositing a radiation-modifiable layer on the substrate and for depositing a self-assembled monolayer on the radiation-modifiable layer; Substrate processing equipment.

2. 10. The substrate processing apparatus of claim 1, wherein the memory comprises a program that, when executed by the control system, operates a precursor delivery and removal system to remove a portion of the first precursor from the reaction chamber after the first precursor is delivered to the reaction chamber.

3. 3. The substrate processing apparatus of claim 2, wherein the precursor delivery and removal system comprises one or more reaction chamber valves for delivering and removing a gaseous second precursor to and from the reaction chamber, and the selective deposition process stored in the memory delivers a second precursor to the precursor delivery and removal system and into the reaction chamber that reacts with one of the radiation-modified layer portion and the unmodified layer portion and does not react with the other of the radiation-modified layer portion and the unmodified layer portion into the reaction chamber to create a sacrificial masking layer.

4. The substrate processing apparatus of claim 3 , wherein the selective deposition method stored in the memory further comprises operating the precursor delivery 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 selective deposition device is constructed and arranged to selectively deposit metal on one of the radiation modified layer portions and the unmodified layer portions.

6. The substrate processing apparatus of claim 1 , wherein the precursor delivery and removal system of the selective deposition apparatus is constructed and arranged to deliver a metal halide into the reaction chamber.

7. 10. The substrate processing apparatus of claim 1, wherein the selective deposition apparatus precursor delivery and removal system is constructed and arranged to deliver a precursor comprising a metal from the group comprising 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) into the reaction chamber.

8. The substrate processing apparatus of claim 1 , wherein the precursor delivery and removal system of the selective deposition apparatus is constructed and arranged to deliver a precursor comprising an oxidizer into the reaction chamber.

9. The substrate processing apparatus of claim 1 , wherein the precursor delivery and removal system of the selective deposition apparatus is constructed and arranged to deliver a silicon-containing precursor into the reaction chamber.

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

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

12. The substrate processing apparatus of claim 1 , wherein the radiation-modifiable layer deposition apparatus comprises a rotatable substrate table for rotating the substrate, and a liquid dispenser for supplying a liquid to a surface of the substrate.

13. a fab input / output port for transporting substrates between the substrate processing equipment and a semiconductor fab; a radiation-modifiable layer deposition apparatus for depositing a radiation-modifiable layer on the substrate; a control system operatively coupled to the substrate handler, the radiation-modifiable layer deposition device, and the selective deposition device, the control system comprising a memory comprising a program; When the program is executed by the control system, controlling the substrate handler to pick up a substrate from the fab input / output port and move it to the radiation-modifiable layer deposition apparatus; controlling the radiation-modifiable layer deposition apparatus to deposit a radiation-modifiable layer on the substrate; controlling the substrate handler to pick up the substrate from the radiation-modifiable layer deposition apparatus and move it via the lithographic input / output port to a lithographic projection apparatus, after locally modifying the radiation-modifiable layer on the substrate with exposure radiation of the lithographic projection apparatus; controlling the substrate handler to pick up the substrate via the lithography input / output port and move it to the selective deposition apparatus; controlling the selective deposition apparatus to deliver into the reaction chamber a first precursor selected to react with one of the radiation-modified layer portion and the unmodified layer portion and not react with the other of the radiation-modified layer portion and the unmodified layer portion to create the sacrificial masking layer; The substrate processing apparatus of claim 1 , further comprising: a substrate handling device configured to: control the substrate handler to pick up the substrate from the selective deposition device and move it to the fab input / output port;

14. 1. A method of treating a substrate to create a sacrificial masking layer, comprising: Providing a substrate comprising a radiation-modifiable layer in a lithographic projection apparatus for locally modifying the radiation-modifiable layer; locally patterning the radiation-modifiable layer of the substrate with exposure radiation of the lithographic projection apparatus to modify the radiation-modifiable layer exposed to the radiation; transferring the substrate from the lithographic projection apparatus to a reaction chamber of a selective deposition apparatus; a reaction chamber for reacting with one of the radiation-modified layer portion and the unmodified layer portion to produce the sacrificial masking layer; providing a first precursor selected to be non-reactive with the other of Including, modifying the radiation-modifiable layer includes depositing a self-assembled monolayer on the radiation-modifiable layer and removing one or more functional groups from the self-assembled monolayer by using EUV radiation. Methods for treating substrates.

15. 15. The method of treating a substrate according to claim 14, wherein the radiation-modifiable layer has a thickness of at least one monolayer.

16. 15. The method of treating a substrate according to claim 14, wherein the radiation-modifiable layer has a thickness of two or more monolayers.

17. A method of treating a substrate according to claim 14, wherein the radiation-modifiable layer has a thickness of from 0.1 to 20 nm.

18. 15. The method of claim 14, wherein after a first precursor selected to react with one of the radiation-modified layer portion and the unmodified layer portion is provided, a precursor delivery and removal system removes unreacted portions of the first precursor and / or reaction by-products from the reaction chamber.

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

20. 20. The method of claim 19, wherein after the second precursor is delivered, the precursor delivery and removal system removes unreacted portions of the second precursor and / or reaction by-products from the reaction chamber.

21. 1. A method of treating a substrate to produce a patterned substrate, comprising: Producing a sacrificial masking layer by the substrate processing method of claim 14; Etching the substrate through the sacrificial masking layer; and removing the sacrificial masking layer.

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