Photoresist layer surface treatment and method for forming photoresist pattern

Abstract

The present application relates to a method for treating a surface of a photoresist layer, a capping layer, and forming a photoresist pattern. Specifically, a method for forming a pattern in a photoresist layer includes forming a photoresist layer above a substrate, and reducing the moisture or oxygen absorption characteristics of the photoresist layer. The photoresist layer is selectively exposed to actinic radiation to form a latent pattern, and the latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern.

Description

[0001] Related Applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 002,297 filed on March 30, 2020 and U.S. Provisional Patent Application No. 63 / 026,695 filed on May 18, 2020, the entire contents of which are incorporated herein by reference. Background Art

[0003] As consumer devices become smaller in response to consumer demand, the size of the individual components of these devices must also decrease. Semiconductor devices that constitute the main components of devices such as mobile phones, computer tablets, etc. have been forced to become smaller and smaller, which in turn has forced the size of the individual devices (e.g., transistors, resistors, capacitors, etc.) within the semiconductor devices to decrease as well.

[0004] One enabling technology used in the manufacture of semiconductor devices is the use of photolithographic materials. Such materials are applied to the surface of the layer to be patterned and then exposed to energy that has itself been patterned. Such exposure changes the chemical and physical properties of the exposed areas of the photosensitive material. This modification, and the lack of modification in the unexposed areas of the photosensitive material, can be exploited to remove one area without removing another area.

[0005] However, as the size of individual devices decreases, the process window for lithographic processing becomes increasingly tighter. Thus, advances in the field of lithographic processing are necessary to maintain the ability to scale down devices, and further improvements are needed to meet the desired design standards so that the march toward smaller and smaller components can be maintained. Summary of the invention

[0006] Some embodiments of the present disclosure provide a method for forming a pattern in a photoresist layer, the method comprising: forming a photoresist layer above a substrate; reducing the moisture or oxygen absorption characteristics of the photoresist layer; selectively exposing the photoresist layer to actinic radiation to form a latent pattern; and developing the latent pattern to form a pattern by applying a developer to the selectively exposed photoresist layer.

[0007] Other embodiments of the present disclosure provide a method for manufacturing a semiconductor device, the method comprising: forming a photoresist layer above a substrate, comprising: combining a first precursor and a second precursor in a gaseous state to form a photoresist material, and depositing the photoresist material above the substrate; reducing the moisture or oxygen absorption characteristics of the photoresist layer; selectively exposing the photoresist layer to actinic radiation to form a latent pattern in the photoresist layer; developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern in the photoresist layer; and extending the pattern in the photoresist layer into the substrate.

[0008] Still other embodiments of the present disclosure provide a method for manufacturing a semiconductor device, the method comprising: depositing a photoresist composition comprising a first organic metal compound and a second compound over a substrate surface by atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form a photoresist layer; reducing the moisture or oxygen absorption characteristics of the photoresist layer; selectively exposing the photoresist layer to actinic radiation to form a latent pattern; developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern exposing a portion of the substrate surface; and removing a portion of the substrate surface exposed by the development. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The present disclosure will be best understood from the following detailed description when read in conjunction with the accompanying drawings. It is emphasized that, in accordance with standard practice in the industry, various features are not drawn to scale and are used for illustration purposes only. In fact, the size of the various features may be arbitrarily increased or reduced for clarity of discussion.

[0010] Figure 1 The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0011] Figure 2A and Figure 2B A process flow for manufacturing a semiconductor device according to an embodiment of the present disclosure is shown.

[0012] Figure 3 The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0013] Figure 4A and Figure 4B The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0014] Figure 5A , Figure 5B , Figure 5C and Figure 5DThe process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0015] Fig. 6A , Figure 6B , Figure 6C , Fig.6D , Fig. 6E and Fig. 6F The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0016] Figure 7 The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0017] Figure 8 The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0018] Fig.9A , Fig. 9B and Fig. 9C An organometallic precursor according to an embodiment of the present disclosure is shown.

[0019] Fig.10 A photoresist deposition apparatus according to some embodiments of the present disclosure is shown.

[0020] Fig.11 The reaction a photoresist layer undergoes due to exposure to actinic radiation and heat according to one embodiment of the present disclosure is shown.

[0021] Fig. 12A A surface treatment operation according to one embodiment of the present disclosure is shown.

[0022] Fig. 12B A cap layer forming operation according to one embodiment of the present disclosure is shown.

[0023] Fig.13 The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0024] Fig.14A and Fig. 14B The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0025] Fig.15A , Fig. 15B , Fig. 15C and Fig.15D The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0026] Fig.16A , Fig. 16B , Fig. 16C , Fig.16D , Fig.16E and Fig.16FThe process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0027] Fig.17 The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0028] Fig.18 The process stages are shown in sequential operation according to one embodiment of the present disclosure. DETAILED DESCRIPTION

[0029] It should be understood that the following disclosure provides many different embodiments or examples for realizing the different features of the present disclosure. Specific embodiments or examples of components and arrangements are described below to simplify the present disclosure. Of course, these are only examples and are not intended to be limiting. For example, the size of the element is not limited to the disclosed range or value, but may depend on the process conditions and / or the desired characteristics of the device. In addition, in the following description, forming a first feature above or on a second feature may include an embodiment in which the first feature and the second feature are formed in direct contact, and may also include an embodiment in which an additional feature inserted between the first feature and the second feature may be formed so that the first feature and the second feature may not be in direct contact. For simplicity and clarity, various features may be arbitrarily drawn in different proportions.

[0030] In addition, for ease of description, spatially relative terms such as "below", "below", "lower", "above", "upper", etc. may be used herein to describe the relationship of one element or feature to another element or features as shown in the figure. In addition to the orientation depicted in the figure, spatially relative terms are also intended to cover different orientations of the device in use or operation. The device can be oriented in other ways (rotated 90 degrees or in other orientations), and the spatially relative descriptors used herein can be interpreted accordingly. In addition, the term "made of" can mean "including" or "consisting of".

[0031] As the semiconductor industry has progressed to nanotechnology process nodes in pursuit of higher device density, higher performance and lower cost, there are challenges in reducing semiconductor feature size. Extreme ultraviolet lithography (EUVL) has been developed to form smaller semiconductor device feature sizes and increase device density on semiconductor wafers. In order to improve EUVL, it is necessary to increase wafer exposure throughput. Wafer exposure throughput can be increased by increasing exposure power or increasing resist photospeed (sensitivity).

[0032] Metal-containing photoresists are used in extreme ultraviolet lithography because metals have high absorption capacity for EUV radiation. However, metal-containing photoresists absorb surrounding moisture and oxygen, which can reduce pattern resolution. The absorption of moisture and oxygen can trigger a crosslinking reaction in the photoresist layer, thereby reducing the solubility of the unexposed areas in the photoresist to the photoresist developer. In addition, the volatile precursors in the photoresist layer can be degassed before radiation exposure and development operations, which will cause the quality of the photoresist layer to change over time and can cause contamination of semiconductor device processing chambers, processing equipment, and other semiconductor wafers. Moisture and oxygen absorption of the photoresist layer and degassing of the photoresist negatively affect lithography performance and increase defects.

[0033] To prevent moisture and oxygen absorption and photoresist degassing, embodiments of the present disclosure treat the surface of the photoresist layer or form a capping layer over the photoresist layer, such as Figure 1 The surface treatment operation according to the present disclosure includes modifying the ligands in the metal-containing photoresist to convert the hydrophilic end groups on the surface of the ligands in the photoresist layer into hydrophobic end groups.

[0034] In some embodiments, the hydrophilic ligand end groups at the upper surface of the photoresist layer are replaced with hydrophobic end groups. In some embodiments, the photoresist layer is treated with plasma or subjected to heat treatment to change the hydrophilic ligand end groups to hydrophobic end groups.

[0035] In other embodiments, a capping layer is deposited on the photoresist layer, such as Figure 1 In some embodiments, the capping layer is a single layer. In some embodiments, the capping layer is a dielectric layer.

[0036] The surface treatment and capping layer protect the photoresist layer from exposure to ambient moisture and oxygen and inhibit outgassing, thereby stabilizing the photoresist layer and reducing defects. The surface treatment and capping layer improve the developer dispersion on the photoresist surface, thereby reducing scum and bridge defects.

[0037] Figure 2A and Figure 2B 1 shows a process flow 100 for manufacturing a semiconductor device according to an embodiment of the present disclosure. In some embodiments, in operation S110, a resist is applied to a surface of a layer to be patterned or a substrate 10 to form a resist layer 15, such as Figure 3In some embodiments, the resist is a metal-containing photoresist formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD). In other embodiments, the metal-containing photoresist layer is formed by a spin coating method. In some embodiments, a surface treatment S115a is performed on the resist layer 15 to form a surface-treated layer 20a, such as Figure 2A and Figure 4A The surface treatment S115a changes the surface of the resist layer 15 from a hydrophilic surface to a hydrophobic surface.

[0038] In some embodiments, after the surface treatment operation S115a, the resist layer 15 undergoes a first heating operation S120. In some embodiments, the first heating operation S120 includes heating the resist layer 15 at a temperature between about 40° C. and about 150° C. for about 10 seconds to about 10 minutes during the first heating operation S120. In some embodiments, before performing the surface treatment S115a on the resist layer 15, the resist layer 15 undergoes the first heating operation S120.

[0039] In some embodiments, Figure 2B and Figure 4B As shown, in operations S125a, S125b, a capping layer 20b is formed over the resist layer 15. In some embodiments, the capping layer 20b is formed before the first heating operation S120. In other embodiments, the capping layer forming operation S125b is performed after the first heating operation S120. In some embodiments, during the first heating operation S120, the resist layer 15 is heated at a temperature between about 40° C. and about 150° C. for about 10 seconds to about 10 minutes.

[0040] Later in Figure 2A and Figure 2B In operation S130, the resist layer 15 and the surface treated layer 20a or the resist layer 15 and the cap layer 20b are selectively exposed to actinic radiation 45 / 97 (see Figure 5A , Figure 5B , Figure 5C and Figure 5D). The resist layer 15 is exposed to actinic radiation 45 / 97 through the surface treated layer 20a or the cap layer 20b. In some embodiments, the actinic radiation 45 / 97 is not substantially absorbed by the surface treated layer 20a or the cap layer 20b. In some embodiments, the photoresist layer 15 is selectively or patterned exposed to ultraviolet radiation. In some embodiments, the ultraviolet radiation is deep ultraviolet radiation (DUV). In some embodiments, the ultraviolet radiation is extreme ultraviolet (EUV) radiation. In some embodiments, the resist layer 15 is selectively or patterned exposed to an electron beam. In some embodiments, the resist layer 15 is a photoresist layer that is photosensitive to actinic radiation 45 / 97, and the cap layer 20b is not a photoresist layer and is non-photosensitive to actinic radiation 45 / 97.

[0041] A photoresist layer according to the present disclosure is a layer that undergoes a chemical reaction upon absorption of actinic radiation resulting in a change in the solubility of the portion of the photoresist layer exposed to the actinic radiation in a developer as compared to the portion of the photoresist layer not exposed to the actinic radiation. A layer that is not photosensitive to actinic radiation does not substantially undergo a chemical reaction upon exposure to actinic radiation that changes the solubility of the layer in a developer.

[0042] like Figure 5A and Figure 5B As shown, in some embodiments, exposure radiation 45 passes through photomask 30 before irradiating photoresist layer 15. In some embodiments, photomask 30 has a pattern to be replicated in photoresist layer 15. In some embodiments, the pattern is formed by an opaque pattern 35 on photomask substrate 40. Opaque pattern 35 can be formed of a material that is opaque to ultraviolet radiation (e.g., chrome), while photomask substrate 40 is formed of a material that is transparent to ultraviolet radiation (e.g., fused silica).

[0043] In some embodiments, extreme ultraviolet lithography is used to perform selective or patterned exposure of the photoresist layer 15 to form exposed areas 50 and unexposed areas 52. Figure 5C and Figure 5DAs shown, in some embodiments, a reflective photomask 65 is used to form patterned exposure light in an EUV lithography operation. The reflective photomask 65 includes a low thermal expansion glass substrate 70 on which a reflective multilayer 75 of Si and Mo is formed. A cap layer 80 and an absorption layer 85 are formed on the reflective multilayer 75. A rear conductive layer 90 is formed on the back side of the low thermal expansion substrate 70. EUV radiation 95 is directed toward the reflective photomask 65 at an incident angle of about 6°. A portion 97 of the EUV radiation is reflected by the Si / Mo multilayer 75 toward the photoresist-coated substrate 10, while a portion of the EUV radiation incident on the absorption layer 85 is absorbed by the photomask. In some embodiments, additional optical devices including mirrors are located between the reflective photomask 65 and the photoresist-coated substrate 10.

[0044] In some embodiments, exposure to radiation is performed by placing the photoresist coated substrate in a lithography tool. The lithography tool includes a photomask 30 / 65, optics, an exposure radiation source that provides radiation 45 / 97 for exposure, and a movable stage for supporting and moving the substrate under the exposure radiation.

[0045] In some embodiments, optics (not shown) are used in the lithography tool to expand, reflect, or otherwise control the radiation 45 / 97 before or after it is patterned by the photomask 30 / 65. In some embodiments, the optics include one or more lenses, mirrors, filters, and combinations thereof to control the radiation 45 / 97 along its path.

[0046] In some embodiments, the radiation is electromagnetic radiation, such as g-line (wavelength of about 436 nm), i-line (wavelength of about 365 nm), ultraviolet radiation, far ultraviolet radiation, extreme ultraviolet, electron beam, etc. In some embodiments, the radiation source is selected from the group consisting of: mercury vapor lamp, xenon lamp, carbon arc lamp, KrF excimer laser (wavelength of 248 nm), ArF excimer laser (wavelength of 193 nm), F2 excimer laser (wavelength of 157 nm), or CO2 laser excited Sn plasma (extreme ultraviolet, wavelength of 13.5 nm).

[0047] The amount of electromagnetic radiation can be characterized by fluence or dose, which is obtained by integrating the radiation flux over the exposure time. Suitable radiation fluence ranges from about 1 mJ / cm 2 About 150mJ / cm 2 , in other embodiments, about 2 mJ / cm 2 About 100mJ / cm 2 , and in other embodiments about 3 mJ / cm 2to about 50mJ / cm 2 Those of ordinary skill in the art will recognize that additional ranges of radiation fluence within the explicit ranges above are contemplated and within the present disclosure.

[0048] In some embodiments, selective or patterned exposure is performed by scanning an electron beam. Using electron beam lithography, the electron beam induces secondary electrons that modify the irradiated material. High resolution can be achieved using electron beam lithography and the metal-containing resists disclosed herein. The electron beam can be characterized by the energy of the beam, and a suitable energy range is from about 5V to about 200kV (kilovolts) in some embodiments, and from about 7.5V to about 100kV in other embodiments. The range of the proximity correction beam dose at 30kV is about 0.1μC / cm in some embodiments. 2 to about 5μC / cm 2 , in other embodiments, about 0.5 μC / cm 2 to about 1μC / cm 2 , and in other embodiments about 1 μC / cm 2 to about 100μC / cm 2 One of ordinary skill in the art can calculate corresponding doses at other beam energies based on the teachings herein, and will recognize that additional ranges of electron beam characteristics within the explicit ranges above are contemplated and within the present disclosure.

[0049] In some embodiments, exposure of the resist layer 15 uses immersion lithography techniques. In such techniques, an immersion medium (not shown) is placed between the final optical device and the photoresist layer, and the exposing radiation 45 passes through the immersion medium.

[0050] The regions of the resist layer exposed to the radiation 50 undergo a chemical reaction, thereby changing its susceptibility to removal in a subsequent development operation S150. In some embodiments, the portions of the resist layer exposed to the radiation 50 undergo a reaction that makes the exposed portions more easily removed during the development operation S150. In other embodiments, the portions of the resist layer exposed to the radiation 50 undergo a reaction that makes the exposed portions resistant to removal during the development operation S150.

[0051] Next, in operation S140, the resist layer 15 undergoes a second heating or post-exposure bake (PEB). In some embodiments, the resist layer 15 is heated at a temperature of about 50°C to about 250°C for about 20 seconds to about 300 seconds. In some embodiments, the post-exposure bake is performed at a temperature in the range of about 100°C to about 230°C, and in other embodiments, the post-exposure bake is performed at a temperature in the range of about 150°C to about 200°C. In some embodiments, the post-exposure bake operation S140 causes the reaction product of the first compound or the first precursor and the second compound or the second precursor in the resist layer to crosslink.

[0052] The selectively exposed resist layer 15 is then developed in operation S150. In some embodiments, the resist layer 15 is developed by applying a solvent-based developer 57 to the selectively exposed resist layer. Fig. 6A and Figure 6B As shown, a liquid developer 57 is supplied from a dispenser 62 to the resist layer 15 and the surface-treated layer 20a or the resist layer 15 and the capping layer 20b, respectively. In some embodiments, the exposed portion 50 of the photoresist undergoes a cross-linking reaction due to exposure to actinic radiation or post-exposure baking, and the unexposed portion of the photoresist layer 52 is removed by the developer 57, thereby forming an opening pattern 55 in the photoresist layer 15 to expose the substrate 10, as shown in FIG. Figure 7 In some embodiments, the surface treated layer 20a and the capping layer 20b are removed during the development operation.

[0053] In some embodiments, the resist developer 57 comprises a solvent and an acid or a base. In some embodiments, the concentration of the solvent is about 60 wt % to about 99 wt % based on the total weight of the resist developer. The concentration of the acid or base is about 0.001 wt % to about 20 wt % based on the total weight of the resist developer. In certain embodiments, the concentration of the acid or base in the developer is about 0.01 wt % to about 15 wt % based on the total weight of the resist developer.

[0054] In some embodiments, the developer 57 is applied to the resist layer 15 using a spin coating process. In the spin coating process, the developer 57 is applied to the resist layer 15 from above the resist layer 15 while the resist-coated substrate is rotating, such as Fig. 6AIn some embodiments, the developer is supplied at a rate between about 5 ml / min and about 800 ml / min while the substrate coated with the photoresist is rotated at a speed between about 100 rpm and about 2000 rpm. In some embodiments, the developer is at a temperature between about 10° C. and about 80° C. In some embodiments, the developing operation lasts between about 30 seconds and about 10 minutes.

[0055] In some embodiments, the developer 57 is an organic solvent. The organic solvent can be any suitable solvent. In some embodiments, the solvent is one or more selected from the following: propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, 4-methyl-2-pentanol, acetone, methyl ethyl ketone, dimethylformamide (DMF), isopropyl alcohol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (MIBC), n-butyl acetate (nBA), 2-heptanone (MAK), tetrahydrofuran (THF) and dioxane.

[0056] Although a spin coating operation is a suitable method for developing the photoresist layer 15 after exposure, it is intended to be illustrative and not intended to be limited to this embodiment. Instead, any suitable developing operation may alternatively be used, including an immersion process, a puddle process, and a spray coating method. All such developing operations are included within the scope of the embodiment.

[0057] In some embodiments, a dry developer 105 is applied to the selectively exposed resist layer 15 and the surface treated layer 20a or cap layer 20b, such as Figure 6C and Fig.6D As shown. In some embodiments, the dry developer 105 is plasma or chemical vapor, and the dry development operation S150 is a plasma etching or chemical etching operation. Dry development uses differences related to composition, degree of crosslinking, and film density to selectively remove the desired portion of the resist. In some embodiments, the dry development process uses a mild plasma (high pressure, low power) or a heat treatment in a heated vacuum chamber, while making the dry development chemical (e.g., BCl3, BF3 or other Lewis acids) flow in a gaseous state. In some embodiments, BCl3 removes unexposed material, leaving a pattern of the exposed film, which is transferred to the lower layer by a plasma-based etching process.

[0058] In some embodiments, dry development includes a plasma process, including transformer coupled plasma (TCP), inductively coupled plasma (ICP), or capacitively coupled plasma (CCP). In some embodiments, the plasma process is performed for about 1 second to about 3000 seconds at a pressure in the range of about 5 mTorr to about 20 mTorr, a power level of about 250 W to about 1000 W, a temperature in the range of about 0° C. to about 300° C., and a flow rate of about 100 sccm to about 1000 sccm.

[0059] In some embodiments, after the post-exposure bake operation S140 and before the development operation S150, the surface treated layer 20a or the capping layer 20b is removed; and then Fig. 6E The wet development operation shown or Fig. 6F The dry developing operation shown performs the developing. In some embodiments, the surface treated layer 20a or the capping layer 20b is removed by a suitable solvent or a suitable dry etchant.

[0060] The developing operation S150 provides a pattern 55 in the photoresist layer, thereby exposing a portion of the substrate 10, such as Figure 7 After the development operation, additional processing is performed while the patterned photoresist layers 15, 50 are in place. For example, in some embodiments, an etching operation using dry etching or wet etching is performed to transfer the pattern of the resist layers 15, 50 to the underlying substrate 10, thereby forming a recess 55', such as Figure 8 As shown. The substrate 10 has a different etching resistance than the resist layer 15. In some embodiments, the etchant is more selective to the substrate 10 than to the resist layer 15. In some embodiments, the patterned resist layers 15, 50 are at least partially removed during the etching operation. In other embodiments, after etching the substrate 10 by selective etching, the patterned resist layers 15, 50 are removed using a suitable resist stripping solvent or by a resist plasma ashing operation.

[0061] In some embodiments, substrate 10 includes a single crystal semiconductor layer at least on a surface portion thereof. Substrate 10 may include a single crystal semiconductor material, such as but not limited to Si, Ge, SiGe, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs, GaSbP, GaAsSb, and InP. In some embodiments, substrate 10 is a silicon layer of a SOI (silicon on insulator) substrate. In certain embodiments, substrate 10 is made of crystalline Si.

[0062] The substrate 10 may include one or more buffer layers (not shown) in its surface region. The buffer layer may be used to gradually change the lattice constant from the lattice constant of the substrate to the lattice constant of the subsequently formed source / drain region. The buffer layer may be formed of an epitaxially grown single crystalline semiconductor material such as, but not limited to, Si, Ge, GeSn, SiGe, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs, GaSbP, GaAsSb, GaN, GaP, and InP. In one embodiment, a silicon germanium (SiGe) buffer layer is epitaxially grown on the silicon substrate 10. The germanium concentration of the SiGe buffer layer may increase from 30 atomic % of the bottommost buffer layer to 70 atomic % of the topmost buffer layer.

[0063] In some embodiments, the substrate 10 includes one or more layers of at least one metal, metal alloy, and metal having the formula MX a wherein M is a metal and X is N, S, Se, O, Si, and a is about 0.4 to about 2.5. In some embodiments, substrate 10 comprises titanium, aluminum, cobalt, ruthenium, titanium nitride, tungsten nitride, tantalum nitride, and combinations thereof.

[0064] In some embodiments, substrate 10 comprises a dielectric material having at least the formula MX b wherein M is a metal or Si, X is N or O, and b ranges from about 0.4 to about 2.5. In some embodiments, the substrate 10 comprises silicon dioxide, silicon nitride, aluminum oxide, hafnium oxide, lanthanum oxide, and combinations thereof.

[0065] The photoresist layer 15 is a photosensitive layer patterned by exposure to actinic radiation. Typically, the chemical properties of the photoresist area struck by the incident radiation change in a manner that depends on the type of photoresist used. The photoresist layer 15 is a positive tone resist or a negative tone resist. A positive tone resist refers to a photoresist material that becomes soluble in a developer when exposed to radiation (such as ultraviolet light), while the unexposed (or less exposed) areas of the photoresist are insoluble in the developer. On the other hand, a negative tone resist refers to a photoresist material that becomes insoluble in a developer when exposed to radiation, while the unexposed (or less exposed) areas of the photoresist are soluble in the developer. The areas of the negative tone resist that become insoluble when exposed to radiation may become insoluble due to a cross-linking reaction caused by exposure to radiation.

[0066] In some embodiments, the photoresist layer includes a high sensitivity photoresist composition. In some embodiments, the high sensitivity photoresist composition is highly sensitive to extreme ultraviolet (EUV) radiation.

[0067] In some embodiments, the photoresist layer 15 is made of a photoresist composition comprising a first compound or a first precursor and a second compound or a second precursor combined in a gaseous state. The first precursor or the first compound is an organic metal having the formula: MaRbXc, such as Fig.9A As shown, wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce or Lu; and R is a substituted or unsubstituted alkyl, alkenyl or carboxylate group. In some embodiments, M is selected from the group consisting of Sn, Bi, Sb, In, Te, and combinations thereof. In some embodiments, R is a C3-C6 alkyl, alkenyl or carboxylate. In some embodiments, R is selected from the group consisting of propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, isohexyl, sec-hexyl, tert-hexyl, and combinations thereof. In some embodiments, X is a ligand, ion or other moiety that reacts with a second compound or a second precursor; and 1≤a≤2, b≥1, c≥1, and b+c≤5. In some embodiments, the alkyl, alkenyl or carboxylate groups are substituted with one or more fluorine groups. In some embodiments, the organometallic precursor is a dimer, such as Fig.9A As shown, each monomer unit is connected by an amine group. Each monomer has the following formula: a R b X c , as defined above.

[0068] In some embodiments, R is an alkyl group, such as C n H 2n+1 , wherein n≥3. In some embodiments, R is fluorinated, for example, having the formula C n F x H ((2n+1)-x) In some embodiments, R has at least one β-hydrogen or β-fluorine. In some embodiments, R is selected from the group consisting of isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl and sec-pentyl, and combinations thereof.

[0069] In some embodiments, X is any moiety that is easily replaced by a second compound or a second precursor to produce an M-OH moiety, such as a moiety selected from the group consisting of: amines, including dialkylamino and monoalkylamino; alkoxy; carboxylates, halogens, and sulfonates. In some embodiments, the sulfonate group is substituted with one or more amine groups. In some embodiments, the halide ion is one or more selected from the group consisting of: F, Cl, Br, and I. In some embodiments, the sulfonate group includes a substituted or unsubstituted C1-C3 group.

[0070] In some embodiments, the first organometallic compound or the first organometallic precursor comprises a metal core M + and attached to the metal core M + The ligand L, such as Fig. 9B In some embodiments, the metal core M + For metal oxide. In some embodiments, ligand L includes C3-C12 aliphatic or aromatic groups. Aliphatic or aromatic groups can be unbranched or branched, with cyclic or non-cyclic saturated side groups containing 1-9 carbons, including alkyl, alkenyl and phenyl. The branched group can be further substituted with oxygen or halogen. In some embodiments, C3-C12 aliphatic or aromatic groups include heterocyclic groups. In some embodiments, C3-C12 aliphatic or aromatic groups are attached to metals through ether bonds or ester bonds. In some embodiments, C3-C12 aliphatic or aromatic groups include nitrite and sulfonate substituents.

[0071] In some embodiments, the organometallic precursor or organometallic compound includes secondary hexyltri(dimethylamino)tin, tert-hexyltri(dimethylamino)tin, isohexyltri(dimethylamino)tin, n-hexyltri(dimethylamino)tin, secondary amyltri(dimethylamino)tin, tert-amyltri(dimethylamino)tin, isopentyltri(dimethylamino)tin, n-amyltri(dimethylamino)tin, secondary butyltri(dimethylamino)tin, tert-butyltri(dimethylamino)tin, isobutyltri(dimethylamino)tin, n-butyltri(dimethylamino)tin, secondary butyltri(dimethylamino)tin, isopropyltri(dimethylamino)tin, n-propyltri(dimethylamino)tin, Tris(diethylamino)tin, and similar alkyltri(tert-butoxy)tin compounds, including secondary hexyltri(tert-butoxy)tin, tert-hexyltri(tert-butoxy)tin, isohexyltri(tert-butoxy)tin, n-hexyltri(tert-butoxy)tin, secondary amyltri(tert-butoxy)tin, tert-amyltri(tert-butoxy)tin, isopentyltri(tert-butoxy)tin, n-amyltri(tert-butoxy)tin, tert-butyltri(tert-butoxy)tin, isobutyltri(tert-butoxy)tin, n-butyltri(butoxy)tin, secondary butyltri(butoxy)tin, isopropyltri(dimethylamino)tin / or n-propyltri(butoxy)tin. In some embodiments, the organometallic precursor or organometallic compound is fluorinated. In some embodiments, the boiling point of the organometallic precursor or compound is less than about 200°C.

[0072] In some embodiments, the first compound or first precursor comprises one or more unsaturated bonds that can coordinate with functional groups (such as hydroxyl groups) on the surface of the substrate or intervening underlying layer to improve the adhesion of the photoresist layer to the substrate or underlying layer.

[0073] In some embodiments, the second precursor or second compound is at least one of an amine, a borane, a phosphine, or water. In some embodiments, the amine has the formula N p H n X m , wherein 0≤n≤3, 0≤m≤3, n+m=3 when p is 1, and n+m=4 when p is 2, and each X is independently a halogen selected from the group consisting of: F, Cl, Br and I. In some embodiments, the borane has the formula B p H n X m , wherein 0≤n≤3, 0≤m≤3, n+m=3 when p is 1, and n+m=4 when p is 2, and each X is independently a halogen selected from the group consisting of: F, Cl, Br and I. In some embodiments, the phosphine has the formula P p H n X m, wherein 0≤n≤3, 0≤m≤3, n+m=3 when p is 1, or n+m=4 when p is 2, and each X is independently a halogen selected from the group consisting of F, Cl, Br and I.

[0074] In some embodiments, the second precursor or compound is water, ammonia or hydrazine. The reaction product of water, ammonia or hydrazine with the organometallic precursor or compound can form hydrogen bonds, which raise the boiling point of the reaction product and prevent the discharge of the metal photoresist material, thereby preventing metal contamination. Hydrogen bonds can also help prevent the effect of moisture on the quality of the photoresist layer.

[0075] Fig. 9B The reaction that a metal precursor undergoes in some embodiments as a result of exposure to actinic radiation is shown. As a result of exposure to actinic radiation, the ligand group L is removed from the metal core M of the metal precursor. + The metal precursor cores are separated and two or more metal precursor cores are bonded to each other.

[0076] Fig. 9C Examples of organometallic precursors according to embodiments of the present disclosure are shown. Fig. 9C In the above formula (A), Bz is a phenyl group.

[0077] In some embodiments, the operation S110 of depositing the photoresist composition is performed by a vapor deposition operation. In some embodiments, the vapor deposition operation includes atomic layer deposition (ALD) or chemical vapor deposition (CVD). In some embodiments, ALD includes plasma enhanced atomic layer deposition (PE-ALD), and CVD includes plasma enhanced chemical vapor deposition (PE-CVD), metal organic chemical vapor deposition (MO-CVD); atmospheric pressure chemical vapor deposition (AP-CVD) and low pressure chemical vapor deposition (LP-CVD).

[0078] According to some embodiments of the present disclosure, the resist layer deposition apparatus 200 is Fig.10. In some embodiments, the deposition apparatus 200 is an ALD or CVD apparatus. The deposition apparatus 200 includes a vacuum chamber 205. A substrate support table 210 in the vacuum chamber 205 supports a substrate 10, such as a silicon wafer. In some embodiments, the substrate support table 210 includes a heater. In some embodiments, a first precursor or compound gas supply 220 and a carrier gas / purge gas supply 225 are connected to an inlet 230 in the chamber via a gas line 235, and a second precursor or compound gas supply 240 and a carrier gas / purge gas supply 225 are connected to another inlet 230' in the chamber via another gas line 235'. The chamber is evacuated, and excess reactants and reaction byproducts are removed by a vacuum pump 245 via an outlet 250 and an exhaust line 255. In some embodiments, the flow rates or pulses of precursor gases and carrier / purge gases, the exhaust of excess reactants and reaction byproducts, the pressure within the vacuum chamber 205, and the temperature of the vacuum chamber 205 or the wafer support table 210 are controlled by a controller 260 that is configured to control each of these parameters.

[0079] Depositing the photoresist layer includes combining a first compound or a first precursor and a second compound or a second precursor in a vapor state to form a photoresist composition. In some embodiments, the first compound or a first precursor and the second compound or a second precursor in the photoresist composition are introduced into the deposition chamber 205 (CVD chamber) via inlets 230, 230' at approximately the same time. In some embodiments, the first compound or a first precursor and the second compound or a second precursor are introduced into the deposition chamber 205 (ALD chamber) via inlets 230, 230' in an alternating manner, i.e., one compound or a first precursor is introduced first, then the second compound or a precursor is introduced, and then the one compound or a precursor is introduced alternately and repeatedly, followed by the second compound or a precursor.

[0080] In some embodiments, during the deposition operation, the temperature of the deposition chamber ranges from about 30°C to about 400°C, and in other embodiments is between about 50°C to about 250°C. In some embodiments, during the deposition operation, the pressure in the deposition chamber ranges from about 5 mTorr to about 100 Torr, and in other embodiments is between about 100 mTorr to about 10 Torr. In some embodiments, the plasma power is less than about 1000 W. In some embodiments, the plasma power ranges from about 100 W to about 900 W. In some embodiments, the flow rate of the first compound or precursor and the second compound or precursor ranges from about 100 sccm to about 1000 sccm. In some embodiments, the flow ratio of the organometallic compound precursor to the second compound or precursor is in the range of about 1:1 to about 1:5. Under operating parameters outside the above ranges, unsatisfactory photoresist layer results occur in some embodiments. In some embodiments, photoresist layer formation occurs in a single chamber (one-pot layer formation).

[0081] In a CVD process according to some embodiments of the present disclosure, two or more gas streams of an organometallic precursor and a second precursor are introduced into a deposition chamber 205 of a CVD device in separate inlet paths 230, 235 and 230', 235', where they are mixed and reacted in the gas phase to form a reaction product. In some embodiments, a separate injection inlet 230, 230' or a dual booster nozzle is used to introduce the flow. The deposition device is configured to allow the flows of the organometallic precursor and the second precursor to mix in the chamber, thereby allowing the organometallic precursor and the second precursor to react to form a reaction product. Without limiting the mechanism, function or use of the present disclosure, it is believed that the product from the gas phase reaction becomes larger in molecular weight and is then condensed or otherwise deposited onto the substrate 10.

[0082] In some embodiments, an ALD process is used to deposit the photoresist layer. During ALD, a layer is grown on the substrate 10 by exposing the surface to alternating gaseous compounds (or precursors). In contrast to CVD, the precursors are introduced as a series of continuous, non-overlapping pulses. In each of these pulses, the precursor molecules react with the surface in a self-limiting manner, so that the reaction terminates once all the reaction sites on the surface are consumed. Therefore, the maximum amount of material deposited on the surface after a single exposure to all precursors (the so-called ALD cycle) is determined by the nature of the precursor-surface interaction.

[0083] In one embodiment of the ALD process, in the first half reaction, the organometallic precursor is pulsed to deliver the metal-containing precursor to the surface of the substrate 10. In some embodiments, the organometallic precursor reacts with a suitable underlying substance (e.g., OH or NH functional groups on the surface of the substrate) to form a new self-saturated surface. In some embodiments, excess unused reactants and reaction byproducts are removed by evacuating with a vacuum pump 245 and / or by flowing an inert purge gas. Then, in some embodiments, a second precursor (e.g., ammonia (NH3)) is pulsed into the deposition chamber. NH3 reacts with the organometallic precursor on the substrate to obtain a reaction product photoresist on the substrate surface. The second precursor also forms a self-saturated bond with the underlying reactive substance to provide another self-limiting and saturated second half reaction. In some embodiments, a second purge is performed to remove unused reactants and reaction byproducts. The pulses of the first and second precursors are alternately performed with the intermediate purge operation until the desired thickness of the photoresist layer is achieved.

[0084] In some embodiments, the photoresist layer 15 is formed to a thickness of about 5 nm to about 50 nm, and in other embodiments to a thickness of about 10 nm to about 30 nm. One of ordinary skill in the art will recognize that additional ranges of thickness within the above-defined ranges are expected and within the present disclosure. The thickness can be evaluated using non-contact methods of x-ray reflectivity and / or ellipsometry based on the optical properties of the photoresist layer. In some embodiments, the thickness of each photoresist layer is relatively uniform for ease of handling. In some embodiments, the thickness of the deposited photoresist layer does not vary by more than ±25% of the average thickness, and in other embodiments, the thickness of each photoresist layer does not vary by more than ±10% of the average photoresist layer thickness. In some embodiments, such as high uniformity deposition on a larger substrate, the evaluation of the uniformity of the photoresist layer can be evaluated with a 1 cm edge exclusion, i.e., the layer uniformity of the portion within 1 cm of the edge of the coating is not evaluated. One of ordinary skill in the art will recognize that additional ranges within the above-defined ranges are expected and within the present disclosure.

[0085] In some embodiments, the first and second compounds or precursors are delivered with a carrier gas into the deposition chamber 205. The carrier gas, purge gas, deposition gas, or other process gas may contain nitrogen, hydrogen, argon, neon, helium, or combinations thereof.

[0086] In some embodiments, the organometallic compound comprises tin (Sn), antimony (Sb), bismuth (Bi), indium (In) and / or tellurium (Te) as metal components, however, the present disclosure is not limited to these metals. In other embodiments, additional suitable metals include titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), cobalt (Co), molybdenum (Mo), tungsten (W), aluminum (Al), gallium (Ga), silicon (Si), germanium (Ge), phosphorus (P), arsenic (As), yttrium (Y), lanthanum (La), cerium (Ce), lutetium (Lu), or combinations thereof. The additional metal may be a substitute or supplement for Sn, Sb, Bi, In and / or Te.

[0087] The specific metal used can significantly affect the absorption of radiation. Therefore, the metal component can be selected based on the desired radiation and absorption cross section. Tin, antimony, bismuth, tellurium and indium provide strong absorption of extreme ultraviolet light at 13.5nm. Hafnium provides good absorption of electron beams and extreme ultraviolet radiation. Metal compositions containing titanium, vanadium, molybdenum or tungsten have strong absorption at longer wavelengths to provide, for example, sensitivity to 248nm wavelength ultraviolet light.

[0088] Fig.11 The reactions that components of a photoresist composition undergo due to exposure to actinic radiation and heat are shown according to one embodiment of the present disclosure. Fig.11 2 shows an exemplary chemical structure of a photoresist layer (PR) at different stages of a photoresist patterning process according to an embodiment of the present disclosure. Fig.11 As shown, the photoresist composition includes an organic metal compound, such as SnX2R2, and a second compound, such as ammonia (NH3). When the organic metal compound and ammonia are combined, the organic metal compound reacts with some of the ammonia in the gas phase to form a reaction product with an amine group attached to the metal (Sn) of the organic metal compound. The amine group in the deposited photoresist layer has a hydrogen bond, which can significantly increase the boiling point of the deposited photoresist layer and prevent the degassing of the metal-containing photoresist material, thereby preventing the metal in the metal-containing photoresist from contaminating the deposition chamber and semiconductor device processing equipment. In addition, the hydrogen bond of the amine group can control the influence of moisture on the quality of the photoresist layer.

[0089] In some embodiments, the photoresist composition is an organic polymer-based composition in a solvent that is deposited by a spin coating process followed by a first heating to remove the solvent.

[0090] When subsequently exposed to EUV radiation, the organometallic compound absorbs the EUV radiation and one or more organic R groups are cleaved from the organometallic compound to form an amide compound in the radiation exposed areas. Then, when a post-exposure bake (PEB) is performed, in some embodiments the amide compound is cross-linked via the amine groups, such as Fig.11 In some embodiments, partial cross-linking of the amide metal compound occurs as a result of exposure to extreme ultraviolet radiation.

[0091] In some embodiments, the surface treatment operation S115a is an in-situ operation, wherein the surface treatment is performed in the same processing chamber as the photoresist deposition operation S110. In other embodiments, the surface treatment operation 115a is an ex-situ operation, wherein the surface treatment is performed in a processing chamber different from the photoresist deposition operation S110. In some embodiments, the surface treatment operation S115a includes changing the surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface. In some embodiments, the surface treatment operation S115a includes replacing the end groups of the ligands in the photoresist layer with non-polar organic groups. In some embodiments, the non-polar organic groups include alkyl or aryl groups. In some embodiments, the surface treatment includes converting the hydrophilic end groups on the ligands in the photoresist layer into hydrophobic end groups. In some embodiments, the polar or hydrophilic end groups on the ligands, such as hydroxyl (-OH) end groups, are replaced or converted to non-polar or hydrophobic end groups, such as methyl (-CH3) or phenyl (-C6H5). In some embodiments, the surface treatment comprises reacting the end groups (e.g., -OH groups) of the ligands in the photoresist layer with ammonia, silane, silylamine, alkyl halide, aryl halide, silicon halide, alkylamine, arylamine, carboxyalkyl or carboxyaryl.

[0092] In some embodiments, the -OH end group on the ligand is liganded with the halogenated silane (SiR y X 4-y ) reaction, wherein X is a halogen and R is a ligand. At least one of the halogens reacts with hydrogen and is removed, and the end group is converted to SiR y X 3-y O. In some embodiments, the ligand R is a non-polar alkyl group, and y is 1-3. In some embodiments, the reaction temperature is from about 20°C to about 500°C.

[0093] Fig. 12A FIG. 2 shows a surface treatment operation according to an embodiment of the present disclosure. Fig. 12A As shown, the ligand L in the metal resist has a hydrophilic end group (-OH group). Silylamine (R3SiNH2) reacts with the hydrophilic end group, thereby converting the hydrophilic end group into a hydrophobic end group (silylamino group).

[0094] In some embodiments, the surface treated layer 20a is removed by exposure to ultraviolet radiation including EUV; heat treatment; developer solution; or etching. In some embodiments, the surface treated layer 20a is removed by heating the surface treated layer 20a to a temperature in the range of about 50° C. to about 400° C. In some embodiments, the surface treated layer 20a is removed by exposing the surface treated layer 20a to ultraviolet radiation having a wavelength in the range of about 10 nm to about 400 nm.

[0095] In other embodiments, the capping layer 20b is a thin layer or includes multiple thin layers. In some embodiments, the capping layer 20b (S110) is deposited by chemical vapor deposition (CVD) operation or atomic layer deposition (ALD) operation. The capping layer 20b can be formed by in-situ operation or ectopic operation. In some embodiments, the capping layer 20b is formed in the same chamber as the CVD or ALD resist layer formation operation, i.e., in-situ operation. In some embodiments, the capping layer 20b is a dielectric layer. In some embodiments, the capping layer 20b is made of silicon oxide, silicon nitride, silicon carbide, SiOC, SiON or their multilayer combination. In some embodiments, silicon oxide, silicon nitride, silicon carbide, SiOC, SiON groups are replaced by one or more polar or non-polar alkyl or aryl groups. In some embodiments, silicon oxide, silicon nitride, silicon carbide, SiOC, SiON groups are replaced by tertiary alkyl or tertiary phenyl. In some embodiments, the substituent is a tertiary butyl group.

[0096] In some embodiments, the capping layer 20b is a spin-coated layer, such as hexamethyldisilazane (HMDS), spin-on glass (SOG), polymethylmethacrylate (PMMA) or spin-on carbon (SOC). In such embodiments, the capping layer 20b is formed in a chamber different from the resist layer forming operation (i.e., an ex situ operation). In some embodiments, the capping layer 20b does not include a photoresist top coating used in an immersion lithography process. In some embodiments, the capping layer 20b does not include an organic polymer or HMDS. In some embodiments, the thickness of the capping layer 20b is in the range of about 0.5nm to about 20nm. The thickness of the capping layer 20b below this range may not be sufficient to prevent moisture and oxygen absorption and photoresist degassing; and a thickness exceeding this range may not provide any additional benefits and may interfere with subsequent processing of the resist. In some embodiments, the capping layer is a single layer.

[0097] Fig. 12B FIG. 2 shows a capping layer forming operation according to an embodiment of the present disclosure. Fig. 12BAs shown, the ligand L in the metal resist has a polar hydrophilic end group (-OH group). Silicon oxide substituted by polar or non-polar organic groups such as Si (OR) 4 is deposited above the resist layer. The cap layer reacts with the polar groups (-OH groups) on the surface of the resist layer to form a non-polar hydrophobic end group (-OR group) above the resist layer. In some embodiments, R is an alkyl or phenyl group. The non-polar hydrophobic end group protects the resist layer 15 from ambient moisture by preventing moisture from penetrating through the cap layer 20b.

[0098] In other embodiments, the capping layer 20b is formed by depositing silicon oxide (e.g., SiO2) directly on the resist layer by CVD or ALD. The thickness of SiO2 ranges from about 3 nm to about 20 nm. The SiO2 capping layer 20b protects the resist layer 15 from direct contact with air.

[0099] In some embodiments, the capping layer 20b is removed by: exposure to ultraviolet radiation including EUV; thermal treatment; developer solution; or etching. The capping layer is selected so that it does not negatively affect the absorption of actinic radiation during the selective exposure of the photoresist layer. In some embodiments, the capping layer 20b is removed by heating the capping layer to a temperature in the range of about 50°C to about 400°C. In some embodiments, the capping layer 20b is removed by exposing the capping layer 20b to ultraviolet radiation in the wavelength range of about 10nm to about 400nm.

[0100] In some embodiments, before forming the photoresist layer, a layer 60 to be patterned is disposed over the substrate, such as Fig.13 As shown. In some embodiments, the layer 60 to be patterned is a metallization layer, or a dielectric layer disposed above the metallization layer, such as a passivation layer. In embodiments in which the layer 60 to be patterned is a metallization layer, the layer 60 to be patterned is formed from a conductive material using a metallization process and a metal deposition technique including chemical vapor deposition, atomic layer deposition, and physical vapor deposition (sputtering). Similarly, if the layer 60 to be patterned is a dielectric layer, the layer 60 to be patterned can be formed by dielectric layer formation techniques including thermal oxidation, chemical vapor deposition, atomic layer deposition, and physical vapor deposition.

[0101] 4, then the surface of the photoresist layer is processed to form a surface-treated layer 20a, or a cap layer 20b is formed over the photoresist layer 15, respectively. Fig.14A Or as shown in 514B.

[0102] The photoresist layer 15 is then selectively exposed to actinic radiation 45 to form exposed areas 50 and unexposed areas 52 in the photoresist layer, such as Fig.15A , Fig. 15B , Fig. 15C , Fig.15D As shown and combined in this article FIG. 5A to FIG. 5D As explained herein, in some embodiments, the photoresist is a negative tone photoresist.

[0103] like Fig.16A , Fig. 16B , Fig. 16C , Fig.16D , Fig.16E and Fig.16F As shown in FIG. , the unexposed photoresist area 52 is developed, as described herein with reference to 6A to 6F As explained above, a photoresist opening pattern 55 is formed. Fig.17 shown.

[0104] Then as Fig.18 As shown, the pattern 55 in the photoresist layer 15 is transferred to the layer 60 to be patterned using an etching operation, and as shown in FIG. Figure 7 As illustrated, the photoresist layer is removed to form pattern 55" in layer 60 to be patterned.

[0105] The novel photoresist layer surface treatment or capping layer formation and photolithography patterning method according to the present disclosure provides higher semiconductor device feature resolution and density with higher wafer exposure throughput and reduced defects in a more efficient method compared to conventional exposure techniques. Embodiments of the present disclosure provide stable photoresist-coated substrates, and the stable photoresist-coated substrates have an increased Q time (the amount of time the photoresist can remain on the substrate or layer to be patterned before the photoresist is exposed to actinic radiation to form a latent pattern). Embodiments of the present disclosure prevent moisture and oxygen absorption of the resist layer, and prevent degassing of the resist layer during subsequent processing. Embodiments of the present disclosure prevent metal resist residues from contaminating processing chambers, processing tools and other wafers. Embodiments of the present disclosure provide photoresist films with improved stability.

[0106] One embodiment of the present disclosure is a method for forming a pattern in a photoresist layer, the method comprising forming a photoresist layer above a substrate, and reducing the moisture or oxygen absorption characteristics of the photoresist layer. The photoresist layer is selectively exposed to actinic radiation to form a latent pattern, and the latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern. In one embodiment, the photoresist layer comprises a metal-containing photoresist composition. In one embodiment, the reducing the moisture or oxygen absorption characteristics of the photoresist layer comprises forming a cap layer above the photoresist layer, wherein the cap layer is made of silicon oxide, silicon nitride, silicon carbide, SiOC, SiON, or a multilayer combination thereof. In one embodiment, the cap layer is a single layer. In one embodiment, the cap layer is formed by chemical vapor deposition or atomic layer deposition. In one embodiment, reducing the moisture or oxygen absorption characteristics of the photoresist layer comprises performing a surface treatment on the surface of the photoresist layer. In one embodiment, the surface treatment comprises reacting the end groups of the ligands in the photoresist layer with ammonia, silane, silylamine, alkyl halide, aryl halide, silicon halide, alkylamine, carboxyalkyl or carboxyaryl. In one embodiment, the surface treatment comprises replacing the end groups of the ligands in the photoresist layer with non-polar organic groups. In one embodiment, the surface treatment comprises changing the surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface. In one embodiment, the surface treatment comprises converting the hydrophilic end groups on the ligands in the photoresist layer to hydrophobic end groups. In one embodiment, the actinic radiation is extreme ultraviolet radiation. In one embodiment, the method comprises post-exposure baking of the photoresist layer after selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before developing the latent pattern. In one embodiment, the post-exposure baking is performed at a temperature in the range of 100°C to 500°C. In one embodiment, the surface treatment comprises treating the photoresist with a plasma or heat treating the surface of the photoresist layer. In one embodiment, the surface treated portion of the photoresist layer is removed by exposure to ultraviolet radiation, exposure to extreme ultraviolet radiation, thermal treatment, a developer solution, or etching. In one embodiment, the capping layer is formed by a chemical vapor deposition (CVD) operation or an atomic layer deposition (ALD) operation. In one embodiment, the capping layer is removed by exposure to ultraviolet radiation, exposure to extreme ultraviolet radiation, thermal treatment, a developer solution, or etching. In one embodiment, the capping layer is removed during development of the latent pattern.

[0107] Another embodiment of the present disclosure is a method of manufacturing a semiconductor device, the method comprising forming a photoresist layer over a substrate by combining a first precursor and a second precursor in a vapor state to form a photoresist material, and depositing the photoresist material over a substrate. The moisture or oxygen absorption characteristics of the photoresist layer are reduced. The photoresist layer is selectively exposed to actinic radiation to form a latent pattern in the photoresist layer. The latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern in the photoresist layer, and the pattern in the photoresist layer extends into the substrate. In one embodiment, the first precursor is an organometallic having the formula: M a R b X c , wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, or Lu; R is a substituted or unsubstituted alkyl, alkenyl, or carboxylate group; X is a halide or sulfonate group; and 1≤a≤2, b≥1, c≥1, and b+c≤5; and the second precursor is at least one of an amine, a borane, a phosphine, or water. In one embodiment, the photoresist material is deposited over the substrate by atomic layer deposition (ALD) or chemical vapor deposition (CVD). In one embodiment, reducing the moisture or oxygen absorption characteristics of the photoresist layer includes changing the surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface. In one embodiment, reducing the moisture or oxygen absorption characteristics of the photoresist layer includes forming a capping layer made of silicon oxide, silicon nitride, silicon carbide, SiOC, SiON, or a multilayer combination thereof. In one embodiment, the method includes removing a capping layer or a surface treated portion of a photoresist layer during developing a latent pattern. In one embodiment, reducing the moisture or oxygen absorption characteristics of the photoresist layer includes reacting the end groups of the ligands in the photoresist layer with ammonia, silane, silylamine, alkyl halide, aryl halide, silicon halide, alkylamine, carboxyalkyl or carboxyaryl. In one embodiment, reducing the moisture or oxygen absorption characteristics of the photoresist layer includes replacing the end groups of the ligands in the photoresist layer with non-polar organic groups. In one embodiment, reducing the moisture or oxygen absorption characteristics of the photoresist layer includes converting the hydrophilic end groups on the ligands in the photoresist layer into hydrophobic end groups. In one embodiment, the capping layer is a monolayer.

[0108] Another embodiment of the present disclosure is a method for manufacturing a semiconductor device, the method comprising depositing a photoresist composition comprising a first organometallic compound and a second compound over a substrate surface by atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form a photoresist layer. The moisture or oxygen absorption characteristics of the photoresist layer are reduced. The photoresist layer is selectively exposed to actinic radiation to form a latent pattern. The latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern that exposes a portion of the substrate surface. The portion of the substrate surface exposed by development is removed. In one embodiment, removing a portion of the substrate surface by development includes etching the substrate surface. In one embodiment, the method includes heating the photoresist layer at a temperature in the range of 100° C. to 500° C. after selectively exposing the photoresist layer to form the latent pattern. In one embodiment, reducing the moisture or oxygen absorption characteristics of the photoresist layer includes reacting the end groups of the ligands in the photoresist layer with ammonia, silane, alkyl halide, silicon halide, aminoalkyl or carboxyalkyl. In one embodiment, reducing the moisture or oxygen absorption characteristics of the photoresist layer includes forming a capping layer made of silicon oxide, silicon nitride, silicon carbide, SiOC, SiON or a multilayer combination thereof. In one embodiment, reducing the moisture or oxygen absorption characteristics of the photoresist layer includes replacing the end groups of the ligands in the photoresist layer with non-polar organic groups. In one embodiment, reducing the moisture or oxygen absorption characteristics of the photoresist layer includes changing the surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface. In one embodiment, reducing the moisture or oxygen absorption characteristics of the photoresist layer includes converting the hydrophilic end groups on the ligands in the photoresist layer into hydrophobic end groups. In one embodiment, the capping layer is a monolayer. In one embodiment, the actinic radiation is extreme ultraviolet radiation.

[0109] Another embodiment of the present disclosure is a method, the method comprising forming a resist layer over a substrate, and surface treating a surface of the resist layer or forming a capping layer made of silicon oxide, silicon nitride, silicon carbide, SiOC, SiON, or a multilayer combination thereof over the resist layer. The resist layer is patterned crosslinked, and an uncrosslinked portion of the resist layer is removed during the patterned crosslinking to form a pattern in the resist layer. In one embodiment, the method comprises heating the resist layer after patterned crosslinking and before removing the uncrosslinked portion of the resist layer. In one embodiment, during heating the resist layer, the resist layer is heated at a temperature in the range of 100° C. to 500° C. In one embodiment, removing a portion of the resist layer comprises applying a developer to the patterned crosslinked resist layer. In one embodiment, removing a portion of the resist layer comprises applying plasma to the patterned crosslinked resist layer. In one embodiment, after patterning the resist layer and before removing a portion of the resist layer, a surface treated portion or capping layer of the resist layer is removed. In one embodiment, the surface treated portion of the resist layer or the capping layer is removed by exposure to ultraviolet radiation, exposure to extreme ultraviolet radiation, thermal treatment, a developer solution, or etching. In one embodiment, the resist layer is formed over the substrate by combining a first precursor and a second precursor in a vapor state to form a resist material, wherein the first precursor is an organometallic having the formula: M a R b X c , wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, or Lu; R is a substituted or unsubstituted alkyl, alkenyl, or carboxylate group; X is a halide or sulfonate group; and 1≤a≤2, b≥1, c≥1, and b+c≤5; and the second precursor is at least one of an amine, borane, phosphine, or water. In one embodiment, the resist layer is deposited over the substrate by atomic layer deposition (ALD) or chemical vapor deposition (CVD).

[0110] Another embodiment of the present disclosure is a method for patterning a resist layer, the method comprising depositing a resist layer over a substrate surface by atomic layer deposition (ALD) or chemical vapor deposition (CVD). The resist layer comprises a reaction product of an organic metal compound with at least one of an amine, a borane, a phosphine, and water. The surface of the resist layer is surface treated, or a cap layer is formed over the resist layer. After treating the surface of the resist layer or forming the cap layer, the resist layer is patterned crosslinked to form a latent pattern in the resist layer. The latent pattern is developed by applying a developer to the patterned crosslinked resist layer to form a pattern that exposes a portion of the substrate surface. In one embodiment, the method includes heating the resist layer for the first time before patterned crosslinking. In one embodiment, the surface treatment or the formation of the cap layer is performed before the first heating. In one embodiment, the surface treatment or the formation of the cap layer is performed after the first heating. In one embodiment, the method includes heating the resist layer for the second time after patterned crosslinking. In one embodiment, the second heating of the resist layer is performed at a temperature in the range of 100°C to 500°C. In one embodiment, the method includes removing exposed portions of the substrate surface after developing. In one embodiment, patterning the resist layer cross-linking includes patterning the resist layer to extreme ultraviolet radiation.

[0111] Another embodiment of the present disclosure is a method of manufacturing a semiconductor device, the method comprising depositing a reaction product of a gas phase organometallic compound and a second gas phase compound over a substrate to form a resist layer over the substrate. The organometallic compound has the formula: a R b X c, wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, or Lu; R is a substituted or unsubstituted alkyl, alkenyl, or carboxylate group; X is a halide or sulfonate group; and 1≤a≤2, b≥1, c≥1, and b+c≤5; and the second gas phase compound is at least one of an amine, a borane, a phosphine, or water. The surface of the resist layer is surface treated, or a cap layer is formed over the resist layer. The resist layer is pattern-crosslinked to form a latent pattern in the resist layer. After the resist layer is pattern-crosslinked, the surface-treated portion or the cap layer of the resist layer is removed. The latent pattern is developed by applying a developer to the pattern-by-pattern crosslinked resist layer to form a pattern exposing a surface portion of the substrate. In one embodiment, the surface-treated portion or the cap layer of the resist layer is removed during the development of the latent pattern. In one embodiment, patterning the crosslinking of the resist layer comprises patterning the resist layer to extreme ultraviolet radiation through the surface treated portion or the capping layer of the resist layer, and heating the patterned exposed resist layer. In one embodiment, the patterned exposed resist layer is heated at a temperature in the range of 100°C to 500°C. In one embodiment, a capping layer is formed, and the capping layer is not a photosensitive layer. In one embodiment, the method includes removing the portion of the substrate exposed by development. In one embodiment, the method includes heating the resist layer at a temperature in the range of 40°C to 150°C before patterning the crosslinking of the resist layer. In one embodiment, the surface treatment comprises reacting the end groups of the ligands in the resist layer with ammonia, silane, silylamine, alkyl halide, aryl halide, silicon halide, alkylamine, carboxyalkyl or carboxyaryl. In one embodiment, the surface treatment comprises replacing the end groups of the ligands in the resist layer with non-polar organic groups. In one embodiment, the surface treatment comprises changing the surface of the resist layer from a hydrophilic surface to a hydrophobic surface. In one embodiment, the surface treatment comprises converting the hydrophilic end groups on the ligands in the resist layer into hydrophobic end groups. In one embodiment, the capping layer is a single layer. In one embodiment, the capping layer is made of silicon oxide, silicon nitride, silicon carbide, SiOC, SiON, or a multilayer combination thereof.

[0112] Another embodiment of the present disclosure is a method for patterning a photoresist layer, the method comprising depositing a photoresist layer over a substrate by a vapor deposition operation. The photoresist layer comprises a reaction product of an organometallic compound and a second compound, wherein the second compound is at least one of an amine, a borane, a phosphine, or water. A cap layer is formed over the photoresist layer, wherein the cap layer is made of silicon oxide, silicon nitride, silicon carbide, SiOC, SiON, or a multilayer combination thereof. The photoresist layer is selectively exposed to actinic radiation through the cap layer to form a latent pattern in the photoresist layer. The cap layer is removed, and portions of the photoresist layer that are not exposed to actinic radiation are removed to form a pattern of the remaining portions of the photoresist layer that are exposed to actinic radiation during the selective exposure of the photoresist layer. In one embodiment, the method comprises removing a portion of the substrate exposed by removing a portion of the photoresist layer. In one embodiment, removing a portion of the substrate comprises dry etching the substrate. In one embodiment, removing a portion of the photoresist layer comprises applying plasma to the photoresist layer. In one embodiment, the vapor deposition operation comprises atomic layer deposition or chemical vapor deposition. In one embodiment, the capping layer is formed by chemical vapor deposition or atomic layer deposition. In one embodiment, the method comprises heating the photoresist layer at a temperature in the range of 40°C to 150°C before selectively exposing the photoresist layer to actinic radiation. In one embodiment, the capping layer is formed before heating the photoresist layer at a temperature in the range of 40°C to 150°C. In one embodiment, the capping layer is formed after heating the photoresist layer at a temperature in the range of 40°C to 150°C. In one embodiment, the capping layer is removed during the removal of the portion of the photoresist layer not exposed to the actinic radiation. In one embodiment, the method comprises heating the capping layer and the photoresist layer at a temperature in the range of 100°C to 500°C after selectively exposing the photoresist layer to actinic radiation.

[0113] The features of several embodiments or examples are summarized above so that those skilled in the art can better understand the various aspects of the present disclosure. Those skilled in the art should understand that they can easily use the present disclosure as a basis for designing or modifying other processes and structures to carry out the same purposes and / or achieve the same advantages as the embodiments or examples introduced herein. Those skilled in the art should also recognize that such equivalent constructions do not depart from the spirit and scope of the present disclosure, and that they can make various changes, substitutions and modifications herein without departing from the spirit and scope of the present disclosure.

Claims

1. A method for forming a pattern in a photoresist layer, the method comprising: forming a photoresist layer over the substrate; wherein the photoresist layer comprises a metal-containing photoresist composition, reducing moisture or oxygen absorption characteristics of the photoresist layer; wherein said reducing the moisture or oxygen absorbing properties of said photoresist layer comprises performing a surface treatment on a surface of said photoresist layer, wherein said surface treatment comprises changing said surface of said photoresist layer from a hydrophilic surface to a hydrophobic surface, and selectively exposing said photoresist layer to actinic radiation to form a latent pattern; as well as The latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern.

2. The method of claim 1, wherein the surface treatment comprises reacting the end groups of the ligands in the photoresist layer with ammonia, silane, alkyl halide, silicon halide, aminoalkyl or carboxyalkyl.

3. The method of claim 1, wherein the surface treatment comprises replacing end groups of ligands in the photoresist layer with non-polar organic groups.

4. The method of claim 1, wherein the surface treatment comprises converting hydrophilic end groups on ligands in the photoresist layer into hydrophobic end groups. 5 . The method of claim 1 , wherein the photoresist layer is formed over the substrate by atomic layer deposition (ALD) or chemical vapor deposition (CVD). 6 . The method of claim 1 , further comprising heating the photoresist layer at a temperature ranging from 100° C. to 500° C. after selectively exposing the photoresist layer to form a latent pattern.

7. The method of claim 1, wherein the surface treatment is performed in the same processing chamber as forming a photoresist layer. 8 . The method of claim 1 , further comprising heating the photoresist layer at a temperature in a range of 40° C. to 150° C. after the surface treatment and before the selectively exposing the photoresist layer.

9. A method for manufacturing a semiconductor device, the method comprising: A photoresist layer is formed over the substrate, comprising: combining the first precursor and the second precursor in a gaseous state to form a photoresist material, and depositing the photoresist material over the substrate; reducing moisture or oxygen absorption characteristics of the photoresist layer; wherein reducing the moisture or oxygen absorption characteristics of the photoresist layer comprises changing the surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface; selectively exposing the photoresist layer to actinic radiation to form a latent pattern in the photoresist layer; developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern in the photoresist layer; and The pattern in the photoresist layer is extended into the substrate.

10. The method of claim 9, wherein the first precursor is an organometallic having the formula: M a R b X c wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce or Lu, R is a substituted or unsubstituted alkyl, alkenyl or carboxylate group, X is a halide or sulfonate group, and 1≤a≤2, b≥1, c≥1, and b+c≤5; and The second precursor is at least one of amine, borane, phosphine or water.

11. The method of claim 9, wherein the photoresist material is deposited over the substrate by atomic layer deposition (ALD) or chemical vapor deposition (CVD).

12. The method of claim 9, wherein changing the surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface comprises reacting an end group of a ligand in the photoresist layer with ammonia, silane, alkyl halide, silicon halide, aminoalkyl, or carboxyalkyl.

13. The method of claim 9, wherein changing the surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface comprises replacing terminal groups of ligands in the photoresist layer with non-polar organic groups.

14. The method of claim 9, wherein changing the surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface comprises converting a hydrophilic end group on a ligand in the photoresist layer to a hydrophobic end group.

15. The method of claim 9, wherein changing the surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface is performed in the same processing chamber as forming the photoresist layer.

16. The method of claim 9, further comprising heating the photoresist layer at a temperature in a range of 40°C to 150°C after changing the surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface and before selectively exposing the photoresist layer.

17. A method for manufacturing a semiconductor device, the method comprising: depositing a photoresist composition comprising a first organometallic compound and a second compound over a surface of a substrate by atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form a photoresist layer; reducing moisture or oxygen absorption characteristics of the photoresist layer; wherein said reducing the moisture or oxygen absorbing properties of said photoresist layer comprises reacting the end groups of ligands in said photoresist layer with ammonia, silane, silylamine, alkyl halide, aryl halide, silicon halide, alkylamine, carboxyalkyl or carboxyaryl, and selectively exposing said photoresist layer to actinic radiation to form a latent pattern; developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern exposing a portion of the substrate surface; as well as A portion of the substrate surface exposed by the developing is removed.

18. The method of claim 17, wherein removing a portion of a substrate surface exposed by the developing comprises etching the substrate surface.

19. The method of claim 17, further comprising heating the photoresist layer at a temperature ranging from 100°C to 500°C after selectively exposing the photoresist layer to form a latent pattern.

20. The method of claim 17, further comprising heating the photoresist layer at a temperature in a range of 40°C to 150°C after reducing the moisture or oxygen absorption characteristics of the photoresist layer and before selectively exposing the photoresist layer.

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