Methods for manufacturing a semiconductor device and patterning methods

Abstract

A method for fabricating a semiconductor device, comprising: forming a photoresist layer over a target layer to be patterned, wherein the formation of the photoresist layer comprises: combining a first precursor and a second precursor in a vapor state to form a photoresist material, wherein the first precursor is a metal-organic material having the following formula: MaRbXc where M is one or more selected from the group consisting of Sn, Bi, Sb, In and Te, R is an alkyl group substituted by one or more electron-donating groups (EDG) or electron-withdrawing groups (EWG), X is a halide or sulfonate group, and 1 ≤ a ≤ 2, b ≥ 1, c ≥ 1 and b + c ≤ 4, and the second precursor is one or more selected from the group consisting of water, an amine, a borane and a phosphine; and deposition of the photoresist material over the target layer to be structured;Selective exposure of the photoresist layer with actinic radiation to form a latent pattern; and development of the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern; wherein the first precursor is a dimer linked by NH or O.;

Description

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[0001] This application claims priority over U.S. Preliminary Patent Application No. 63 / 047,350, filed on July 2, 2020, and U.S. Preliminary Patent Application No. 63 / 049,956, filed on July 9, 2020, the entire contents of each of which are incorporated into this document by reference. BACKGROUND

[0002] As consumer devices become ever smaller in response to consumer demand, the size of the individual components of these devices must also be reduced. Semiconductor devices, which are a major component of devices such as mobile phones, computer tablets, and the like, are necessarily becoming smaller, with corresponding pressure on the individual components (e.g., transistors, resistors, capacitors) within the semiconductor devices to also become smaller.

[0003] A fundamental technology used in the manufacturing processes of semiconductor devices is the use of photolithographic materials. These materials are applied to the surface of a layer to be patterned and then exposed to an energy that has itself been patterned. This exposure modifies the chemical and physical properties of the exposed areas of the photosensitive material. This modification, along with the lack of modification in unexposed areas of the photosensitive material, can be exploited to remove one area without removing another.

[0004] However, as the size of individual components has decreased, the process windows for photolithographic processing have become increasingly narrow. Therefore, advances in photolithographic processing are necessary to maintain the ability to miniaturize components, and further improvements are required to meet desired design criteria so that the trend towards ever smaller components can be sustained. List of characters

[0005] The present disclosure is best understood by referring to the following detailed description, which is read in conjunction with the accompanying figures. It is emphasized that, in accordance with standard industry practice, various features are not drawn to scale and are for illustrative purposes only. In fact, the dimensions of the various features may be enlarged or reduced as desired for the clarity of the discussion. Fig. Figure 1 illustrates a process flow for the manufacture of a semiconductor device according to embodiments of the disclosure. Fig. Figure 2 shows a process stage of a sequential process according to an embodiment of the disclosure. The Fig. 3A and Fig. Figure 3B shows a process stage of a sequential process according to an embodiment of the disclosure. The Fig. 4A and Fig. Figure 4B shows a process stage of a sequential process according to an embodiment of the disclosure. Fig. Figure 5 shows a process stage of a sequential process according to an embodiment of the disclosure. Fig. Figure 6 shows a process stage of a sequential process according to an embodiment of the disclosure. Fig. 7A shows metal-organic precursors according to embodiments of the disclosure. Fig. 7B shows metal-organic precursors according to embodiments of the disclosure. Fig. Figure 8 shows a photoresist deposition device according to some embodiments of the disclosure. Fig. Figure 9A shows a reaction to which the photoresist layer is subjected as a result of exposure to actinic radiation and heating, according to an embodiment of the disclosure. Fig. Figure 9B shows a reaction to which the photoresist layer is subjected as a result of exposure to actinic radiation and heating, according to an embodiment of the disclosure. Fig. Figure 10 shows a process stage of a sequential process according to an embodiment of the disclosure. The Fig. 11A and Fig. Figure 11B shows a process stage of a sequential process according to an embodiment of the disclosure. The Fig. 12A and Fig. Figure 12B shows a process stage of a sequential process according to an embodiment of the disclosure. Fig. Figure 13 shows a process stage of a sequential process according to an embodiment of the disclosure. Fig. Figure 14 shows a process stage of a sequential process according to an embodiment of the disclosure. The Fig. 15A, Fig. 15B, Fig. 15C, Fig. 15D, Fig. 15E and Fig. Figure 15F shows various stages of a sequential manufacturing process of a semiconductor device according to an embodiment of the present disclosure. The Fig. 15G, Fig. 15H, Fig. 15I and Fig. Figure 15J shows various stages of a sequential manufacturing process of a semiconductor device according to an embodiment of the present disclosure. DETAILED DESCRIPTION

[0006] It is understood that the following disclosure provides many different embodiments or examples for implementing various features of the disclosure. To simplify the present disclosure, specific embodiments or examples of components and arrangements are described below. These are, of course, merely examples and are not intended to be limiting. For instance, the dimensions of elements are not limited to the disclosed ranges or values ​​but may depend on the process conditions and / or desired properties of the component.Furthermore, the formation of a first feature over or on top of a second feature in the following description may include embodiments in which the first and second features are formed in direct contact, and also embodiments in which additional features can be formed between the first and second features in such a way that the first and second features may not be in direct contact. For the sake of simplicity and clarity, various features may be drawn at different scales.

[0007] Furthermore, spatially relative terms such as "under," "below," "lower," "above," "upper," and the like can be used here to simplify the description and describe the relationship of one element or feature to another element(s) or feature(s), as illustrated in the figures. In addition to the orientation shown in the figures, these spatially relative terms are intended to encompass different orientations of the component in use or operation. The component may be oriented differently (rotated by 90 degrees or in other orientations), and the spatially relative descriptions used here can be interpreted accordingly. Furthermore, the term "made of" can mean either "comprising" or "consisting of."

[0008] As the semiconductor industry has advanced into nanometer-scale process nodes in the pursuit of higher device density, improved performance, and lower costs, challenges exist regarding the reduction of semiconductor feature size. Extreme ultraviolet lithography (EUVL) was developed to create smaller semiconductor feature sizes and increase device density on a semiconductor wafer. To improve EUVL, increasing the wafer exposure throughput is desirable. Wafer exposure throughput can be improved by increasing exposure power or resist exposure speed (sensitivity). Conversely, reducing the extreme ultraviolet (EUV) dose is desirable for cost reduction.

[0009] Metal-containing photoresists are used in extreme ultraviolet (EUV) lithography because metals have a high absorption capacity for extreme ultraviolet radiation, thus increasing the resist exposure speed. However, metal-containing photoresist layers can outgas during processing, which can lead to changes in the photoresist layer's quality over time and the formation of impurities, negatively impacting lithography performance and increasing defects.

[0010] Furthermore, uneven exposure of the photoresist, particularly in deeper sections of the photoresist layer, can lead to an uneven degree of cross-linking. Uneven exposure results from a lower amount of light energy reaching the lower sections of the photoresist layer. This uneven exposure can lead to poor line width roughness (LWR), preventing the formation of a straight-edged resist profile.

[0011] Furthermore, the solvents used in the formation and development of solvent-based photoresists can be toxic. A more environmentally friendly process for forming photoresist layers and subsequent pattern production without the use of toxic solvents is desirable.

[0012] Furthermore, in a spin coating process, only 2-5% of the material spread on the substrate may be used, while the remaining 95-98% is spun off during the process. A photoresist deposition process with high material utilization efficiency is desirable.

[0013] Furthermore, the density of the centrifugally coated photoresist films may not be uniform. Aggregation of the photoresist film may occur in some sections.

[0014] Furthermore, it is desirable that the processes for forming and structuring the photoresist layer significantly reduce or prevent metal contamination of the processing chambers and substrate handling equipment by the metals in metal-containing photoresists.

[0015] In embodiments of the disclosure, the aforementioned problems are solved by depositing a photoresist onto a substrate by a vapor deposition process, including atomic layer deposition (ALD) or chemical vapor deposition (CVD) of the photoresist material. Photoresist layers deposited by a vapor deposition process according to embodiments of the disclosure provide photoresist layers that exhibit a controllable film thickness and high film uniformity and density over a large deposited area. Furthermore, embodiments of the disclosure include solvent-free formation of photoresist layers, thus providing a more environmentally friendly process.Furthermore, in some embodiments, the photoresist deposition process is a one-pot process (performed in a single chamber), thereby increasing manufacturing efficiency and limiting or preventing metal contamination of the processing chambers. In some embodiments, bond dissociation energy (BDE) tuning is used to increase the efficiency of the EUV exposure process.

[0016] Fig. Figure 1 illustrates a process flow 100 for the fabrication of a semiconductor device according to embodiments of the disclosure. In some embodiments, in process S110, a lacquer is applied to a surface of a layer to be structured or a substrate 10 to form a lacquer layer 15, as shown in Fig. Figure 2 shows that in some embodiments, the resist is a metal-containing photoresist formed by CVD or ALD. In some embodiments, the resist layer 15 is then subjected to a first heating process S120 after deposition. In some embodiments, the resist layer is heated to a temperature of about 40 °C to about 120 °C for about 10 seconds to about 10 minutes.

[0017] After the optional first heating process S120 or the varnish deposition process S110, the photoresist layer 15 is selectively treated with actinic radiation 45 / 97 in process S130 (see Fig. 3A and Fig. 3B) exposed. In some embodiments, the photoresist layer 15 is selectively or pattern-wise exposed to ultraviolet radiation. In some embodiments, the ultraviolet radiation can be deep ultraviolet radiation (DUV). In some embodiments, the ultraviolet radiation can be extreme ultraviolet radiation (EUV). In some embodiments, the photoresist layer is selectively or pattern-wise exposed to an electron beam.

[0018] As in Fig. As shown in Figure 3A, in some embodiments the exposure radiation 45 passes through a photomask 30 before irradiating the photoresist layer 15. In some embodiments, the photomask has a pattern that is to be replicated in the photoresist layer 15. In some embodiments, the pattern is formed by an opaque pattern 35 on the photomask substrate 40. The opaque pattern 35 can be made of a material impermeable to ultraviolet radiation, such as chromium, while the photomask substrate 40 is made of a material permeable to ultraviolet radiation, such as quartz glass.

[0019] In some embodiments, the selective or patterned exposure of the photoresist layer 15 to form exposed areas 50 and unexposed areas 52 is carried out using extreme ultraviolet lithography. In some embodiments, a reflective photomask 65 is used to form the structured exposure light during the extreme ultraviolet lithography process, as shown in Fig. Figure 3B shows the reflective photomask 65 enclosing a low-thermal-expansion glass substrate 70 on which a reflective Si / Mo multilayer 75 is formed. A cover layer 80 and an absorber 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. Extreme ultraviolet radiation 95 is directed at the reflective photomask 65 at an angle of incidence of approximately 6°. A portion 97 of the extreme ultraviolet radiation is reflected by the Si / Mo multilayer 75 toward the photoresist-coated substrate 10, while the portion of the extreme ultraviolet radiation incident on the absorber layer 85 is absorbed by the photomask. In some embodiments, additional optics, including mirrors, are located between the reflective photomask 65 and the photoresist-coated substrate.

[0020] In some embodiments, exposure is carried out using radiation by placing the photoresist-coated substrate in a photolithography tool. The photolithography tool includes a photomask 30 / 65, optics, an exposure radiation source to provide the radiation 45 / 97 for exposure, and a movable platform for supporting and moving the substrate under the exposure radiation.

[0021] In some embodiments, the optics (not shown) are used in the photolithography tool to expand, reflect, or otherwise control the radiation before or after the radiation 45 / 97 is structured 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.

[0022] In some embodiments, the radiation is electromagnetic radiation, such as g-line (wavelength of approximately 436 nm), i-line (wavelength of approximately 365 nm), ultraviolet radiation, far-ultraviolet radiation, extreme ultraviolet radiation, electron beams, or the like. In some embodiments, the radiation source is one or more of, for example, a mercury vapor lamp, xenon lamp, carbon arc lamp, a KrF excimer laser (wavelength of 248 nm), an ArF excimer laser (wavelength of 193 nm), an F2 excimer laser (wavelength of 157 nm), or a CO2 laser-excited Sn plasma (extreme ultraviolet radiation, wavelength of 13.5 nm).

[0023] The amount of electromagnetic radiation can be characterized by a fluence or dose, which results from the integrated radiation flux versus the exposure time. Suitable radiation fluences in some embodiments are in the range of approximately 1 mJ / cm². 2 up to about 150 mJ / cm² 2 , in other embodiments of about 2 mJ / cm² 2 up to about 100 mJ / cm² 2 and in other embodiments and of about 3 mJ / cm² 2 up to about 50 mJ / cm² 2 A person skilled in the art understands that additional areas of radiation influences within the foregoing explicit areas are considered and included in the present disclosure.

[0024] In some embodiments, selective or pattern exposure is performed using a scanning electron beam. In electron beam lithography, the electron beam induces secondary electrons that modify the irradiated material. High resolution is achievable using electron beam lithography and the metal-containing resists disclosed herein. Electron beams can be characterized by their energy, and suitable energies range from about 5 V to about 200 kV (kilovolts) in some embodiments and from about 7.5 V to about 100 kV in others. Approximately corrected beam doses at 30 kV are in the range of about 0.1 µC / cm² in some embodiments. 2 up to about 5 µC / cm 2 , in other embodiments of about 0.5 µC / cm 2 up to about 1 µC / cm 2 and in other embodiments of about 1 µC / cm 2 up to approximately 100 µC / cm 2An average person skilled in the art can calculate corresponding doses at other beam energies based on the teachings of this document and understands that additional areas of electron beam properties are considered within the foregoing explicit areas and are contained in the present disclosure.

[0025] The radiation-exposed area 50 of the photoresist layer undergoes a chemical reaction, which alters its susceptibility to removal in a subsequent development process S150. In some embodiments, the section of the photoresist layer exposed to radiation 50 undergoes a reaction that makes the exposed section easier to remove during development process S150. In other embodiments, the section of the photoresist layer exposed to radiation 50 undergoes a reaction that makes the exposed section resistant to removal during development process S150.

[0026] Subsequently, in process S140, the photoresist layer 15 is subjected to a second heating or post-exposure bake (PEB) process. In some embodiments, the photoresist layer 15 is heated to a temperature of approximately 50 °C to approximately 250 °C for approximately 20 to approximately 120 seconds. In some embodiments, the post-exposure bake is carried out at a temperature in the range of approximately 100 °C to approximately 230 °C, and in other embodiments at a temperature in the range of approximately 150 °C to approximately 200 °C. In some embodiments, the post-exposure bake process S140 causes the reaction product of a first compound or precursor and a second compound or precursor to crosslink.

[0027] The selectively exposed photoresist layer is then developed in process S150. In some embodiments, the photoresist layer 15 is developed by applying a solvent-based developer 57 to the selectively exposed photoresist layer. As described in Fig. As shown in Figure 4A, a liquid developer 57 is supplied to the photoresist layer 15 from a dispenser 62. In some embodiments, the exposed sections 50 of the photoresist undergo a crosslinking reaction as a result of exposure to actinic radiation or post-exposure baking, and the unexposed section of the photoresist layer 52 is removed by the developer 57, forming a pattern of openings 55 in the photoresist layer 15 to expose the substrate 20, as shown in Figure 4A. Fig. 5 shown.

[0028] In some embodiments, the photoresist developer 57 includes a solvent and an acid or a base. In some embodiments, the solvent concentration is approximately 60% to approximately 99% by weight, based on the total weight of the photoresist developer. The acid or base concentration is approximately 0.001% to approximately 20% by weight, based on the total weight of the photoresist developer. In certain embodiments, the acid or base concentration in the developer is approximately 0.01% to approximately 15% by weight, based on the total weight of the photoresist developer.

[0029] In some embodiments, the developer 57 is applied to the photoresist layer 15 using a spin-on process. In the spin-on process, the developer 57 is applied to the photoresist layer 15 from above while the photoresist-coated substrate is rotated, as shown in Fig. Figure 4A shows that in some embodiments, the developer 57 is supplied at a rate between approximately 5 ml / min and approximately 800 ml / min, while the photoresist-coated substrate 10 is rotated at a speed between approximately 100 RPM and approximately 2000 RPM. In some embodiments, the developer has a temperature between approximately 10 °C and approximately 80 °C during the development process. The development process lasts between approximately 30 seconds and approximately 10 minutes in some embodiments.

[0030] In some embodiments, 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 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), isopropanol (IPA), tetrahydrofuran (THF), methyl isobutylcarbinol (MIBC), n-butyl acetate (nBA), 2-heptanone (MAK), tetrahydrofuran (THF), and dioxane.

[0031] While the spin-drying process is a suitable method for developing the photoresist layer 15 after exposure, it is intended only for illustrative purposes and does not restrict the embodiment. Instead, any suitable development methods, such as immersion, puddle, and spray processes, can be used. All such development processes are included within the scope of the embodiments.

[0032] In some embodiments, a dry developer 105 is applied to the selectively exposed photoresist layer 15, as in Fig. Figure 4B shows that in some embodiments, the dry developer 105 is a plasma or a chemical vapor, and the dry development process S150 is a plasma etching or a chemical etching process. Dry development utilizes differences in composition, degree of crosslinking, and film density to selectively remove desired sections of the resist. In some embodiments, the dry development process uses either a gentle plasma (high pressure, low power) or a thermal process in a heated vacuum chamber, while a dry development chemistry, such as Cl₂, CHCl₃, CH₂Cl₂, CH₄, CF₄, N₂, BF₃, BCl₃, CCl₄, HCl, O₂, NF₃, NH₃, N₂H₂, HBr, and NO₂, or another Lewis acid, flows in the vapor state. In some embodiments, the BCl₃ removes the unexposed material, leaving a pattern of the exposed film that is transferred to the underlying layers by plasma-based etching processes.

[0033] In some embodiments, dry development includes plasma processes, including transformer-coupled plasma (TCP), inductively coupled plasma (ICP), or capacitively coupled plasma (CCP). In some embodiments, the plasma process is carried out at a pressure in the range of about 5 mTorr to about 20 mTorr, at a power level of about 250 W to about 1000 W, at a temperature in the range of about 0 °C to about 300 °C, and at a flow rate of about 100 to about 1000 sccm for about 1 to about 3000 seconds.

[0034] Following the development process, an additional processing step is performed while the structured photoresist layer 50 is present. For example, in some embodiments, an etching process using dry or wet sets is carried out to transfer the pattern of the photoresist layer 50 to the underlying substrate 10, thereby forming depressions 55', as shown in Fig. Figure 6 shows that the substrate 10 has a different etching resistance than the photoresist layer 15. In some embodiments, the etchant is more selective for the substrate 10 than for the photoresist layer 15.

[0035] In some embodiments, the exposed photoresist layer 15 is at least partially removed during the etching process. In other embodiments, the exposed photoresist layer 15 is removed after etching the substrate 10 by selective etching using a suitable photoresist stripper solvent or by a photoresist plasma ashing process.

[0036] In some embodiments, the substrate 10 encloses a single-crystal semiconductor layer on at least one surface portion thereof. The substrate 10 may, but is not limited to, a single-crystal semiconductor material such as Si, Ge, SiGe, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs, GaSbP, GaAsSb, and InP. In some embodiments, the substrate 10 is a silicon layer of a silicon-on-insulator (SOI) substrate. In certain embodiments, the substrate 10 is made of crystalline Si.

[0037] The substrate 10 can enclose one or more buffer layers (not shown) in its surface region. The buffer layers can serve to gradually change the lattice constant from that of the substrate to that of the subsequently formed source / drain regions. The buffer layers can be formed from epitaxially grown single-crystal semiconductor materials such as Si, Ge, GeSn, SiGe, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs, GaSbP, GaAsSb, GaN, GaP, and InP, but are not limited to these materials. In one embodiment, the silicon germanium (SiGe) buffer layer is epitaxially grown on the silicon substrate 10. The germanium concentration of the SiGe buffer layers can increase from 30 atomic percent for the bottommost buffer layer to 70 atomic percent for the topmost buffer layer.

[0038] In some embodiments, the substrate 10 comprises one or more layers of at least one metal, a metal alloy and a metal nitride / sulfide / oxide / silicide with the formula MX a one, where M is a metal and XN, S, Se, O, Si are, and a is from about 0.4 to about 2.5. In some embodiments, the substrate 10 includes titanium, aluminum, cobalt, ruthenium, titanium nitride, tungsten nitride, tantalum nitride, and combinations thereof.

[0039] In some embodiments, the substrate 10 includes a dielectric material comprising at least one silicon or metal oxide or nitride of the formula MX b one, where M is a metal or Si, XN is or O, and b is in the range of about 0.4 to about 2.5. In some embodiments, the substrate 10 includes silicon dioxide, silicon nitride, aluminum oxide, hafnium oxide, lanthanum oxide, and combinations thereof.

[0040] In some embodiments, a bottom antireflective coating (BARC) layer is formed between the substrate and the metallic photoresist layer 15.

[0041] The photoresist layer 15 is a light-sensitive layer that is structured by irradiation with actinic radiation. Typically, the chemical properties of the photoresist areas exposed to the incident radiation change in a way that depends on the type of photoresist used. Photoresist layers 15 are either positive or negative. A positive photoresist refers to a photoresist material in which, during development, the sections of the photoresist layer exposed to actinic radiation, such as UV light, are removed, while the area of ​​the photoresist that is not (or less) exposed remains on the substrate after the development process.A negative resist, on the other hand, refers to a photoresist material in which, during development, the sections of the photoresist exposed to actinic radiation remain on the substrate after the development process, while the area of ​​the photoresist that is not (or less) exposed is removed during the development process.

[0042] In some embodiments, the photoresist layer 15 consists of a photoresist composition comprising a first compound or first precursor and a second compound or second precursor, combined in a vapor state. The first precursor or first compound is a metal-organic material with the formula: M a R b X c (a, b and c are natural numbers), as in Fig. 7A and Fig. 7B shown, where M is one or more selected from the group consisting of Sn, Bi, Sb, In, and Te; where R is a substituted or unsubstituted alkyl, alkenyl, or carboxylate group. In some embodiments, X is a ligand, an ion, or other grouping that is reactive with the second compound or precursor; and 1 ≤ a ≤ 2, b ≥ 1, c ≥ 1, and b + c ≤ 4 in some embodiments. In certain embodiments, b + c = 4. In some embodiments, the alkyl, alkenyl, or carboxylate group is substituted with one or more fluorine groups. In some embodiments, the organometallic precursor is a dimer, as shown in Fig. Figure 7A shows that each monomer unit is linked by an amine group. In some embodiments, b=c=2. In other embodiments, the organometallic precursor is a dimer, as shown in Figure 7A. Fig. Figure 7B shows each monomer unit linked by oxygen. In some embodiments, b=1 and c=3. Each monomer has a formula: M a R b X c , as described above.

[0043] In some embodiments, R in the formula M includes a R b X c Alkyl groups are incorporated that are substituted by different electron-donating groups (EDGs) and / or electron-withdrawing groups (EWGs) to tune the bond dissociation energy to provide a bond that is cleaved by a low EUV dose. In some embodiments, R is a substituted or unsubstituted C1-C20 alkyl group, including all isomers of C1-C20 alkyl groups. The EDG includes an oxide group (-O -The group includes amino groups (-NH2, -NHR, -NR2, where R = C1-C4 groups and phenyl groups), hydroxyl and alkoxyl groups (-OH, -OR, where R = C1-C4 groups and phenyl groups), acylamido groups (-NHCOR, where R = C1-C4 groups and phenyl groups), alkylthio and sulfhydryl groups (-SH, -SR, where R = C1-C4 groups and phenyl groups), a phenyl group, and carboxylate groups (-(C=O)O-). EWG includes halide groups (-I, -Cl, -Br, -F), ammonium groups (-NR3). + , where R = C1-C4 groups and phenyl groups), nitro groups (-NO2), sulfonic acids and sulfonyl groups (-SO3H, -SO2R, where R = C1-C4 groups and phenyl groups), cyano group (-CN), formyl and acyl groups (-CHO, -COR, where R = C1-C4 groups and phenyl groups), carboxyl and alkoxycarbonyl groups (-CO2H, -CO2R, where R = C1-C4 groups and phenyl groups), and aminocarbonyl groups (-CONH2, -CONHR, -CONR, where R = C1-C4 groups and phenyl groups), where the C1-C4 groups include all isomers of the C1-C4 groups.

[0044] In some embodiments, the first precursor or the first compound with the formula M a R b X c R includes all structural isomers of C1-C4 alkyl groups substituted with a phenyl group, an amino group (-NH2, -NHR, -NR2, where R = C1-C3 alkyl group), hydroxyl groups, and alkoxyl groups (-OH, -OR, where R = C1-C3 alkyl group and a phenyl group). In some embodiments, the first precursor or the first compound with the formula M includes a R b X c R C1-C4 alkyl groups are substituted at the α-C position by one or two phenyl groups, an amino group (-NH2, -NHR, -NR2, where R=C1-, C2- or C3-alkyl group) and alkoxyl groups (-OR, where R=C1-, C2- or C3-alkyl group).

[0045] In some embodiments, X is any grouping that can readily be displaced by the second compound or precursor to generate an M-OH grouping, such as a grouping selected from the group consisting of amines, including dialkylamino and monalkylamino; alkoxy; carboxylates; halogens; and sulfonates. In some embodiments, the sulfonate group is substituted with one or more amine groups. In some embodiments, the halide 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.

[0046] In some embodiments, the first compound or precursor includes one or more unsaturated bonds that can be coordinated with a functional group, such as a hydroxyl group, on the surface of the substrate or an intermediate sublayer to improve the adhesion of the photoresist layer to the substrate or sublayer.

[0047] In some embodiments, the second precursor or compound is one or more selected from the group consisting of water, an amine, a borane, and a phosphine. In some embodiments, the amine has a formula N p H n X m where 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 an independent halogen selected from the group consisting of F, Cl, Br, and I. In some embodiments, the borane has a formula B p H n X mwhere 0 ≤ n ≤ 3, 0 < m ≤ 3, n + m = 3 when p 1, and n + m = 4 when p 2, and each X is an independent halogen selected from the group consisting of F, Cl, Br, and I. In some embodiments, the phosphine has a formula P p H n X m on, where 0 ≤ n ≤ 3, 0 ≤ m ≤ 3, n + m = 3 if p 1, or n + m = 4 if p 2, and each X is an independent halogen selected from the group consisting of F, Cl, Br and I.

[0048] In some embodiments, the second precursor or compound is ammonia or hydrazine. The reaction product of the ammonia or hydrazine and the organometallic precursor or compound can form hydrogen bonds, which raise the boiling point of the reaction product and prevent the emission of the metallic photoresist material, thus preventing metal contamination. The hydrogen bonds can also help to prevent the effects of moisture on the quality of the photoresist layer.

[0049] In some embodiments, process S110 of depositing a photoresist composition is carried out by a vapor deposition process. In some embodiments, the vapor deposition process 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).The deposition of a photoresist layer involves combining the first compound or precursor and the second compound or precursor in a vapor state to form the photoresist composition. In some embodiments, the first compound or precursor and the second compound or precursor of the photoresist composition are introduced into the deposition chamber (CVD chamber) at approximately the same time. In other embodiments, the first compound or precursor and the second compound or precursor are introduced into the deposition chamber (ALD chamber) alternately, i.e., first one compound or precursor, then a second compound or precursor, and subsequently the introduction of one compound or precursor followed by the second compound or precursor is repeated alternately.

[0050] In some embodiments, the temperature of the deposition chamber during the deposition process is between about 30 °C and about 400 °C, and in other embodiments between about 50 °C and about 250 °C. In some embodiments, the pressure in the deposition chamber during the deposition process is in the range of about 5 mTorr to about 100 Torr, and in other embodiments between about 100 mTorr and about 10 Torr. In some embodiments, the plasma power is less than about 1000 W. In some embodiments, the plasma power is in the range of about 100 W to about 900 W. In some embodiments, the flow rate of the first compound or first precursor and the second compound or second precursor is in the range of about 100 sccm to about 1000 sccm.In some embodiments, the ratio of the flux of the precursor of the metal-organic compound to the second compound or the second precursor is in the range of approximately 1:1 to approximately 1:10, and in other embodiments in the range of approximately 1:3 to 1:6. Under operating parameters outside the aforementioned ranges, inadequate photoresist layers are formed in some embodiments. In some embodiments, the photoresist layer is formed in a single chamber (one-pot layer formation).

[0051] In a CVD process according to some embodiments of the disclosure, two or more gas streams of a metal-organic precursor and a second precursor are introduced into the deposition chamber of a CVD device via separate inlet paths, where they mix and react in the gas phase to form a reaction product. In some embodiments, the streams are introduced using separate injection inlets or a dual-chamber shower head. The deposition device is configured such that the streams of the metal-organic precursor and the second precursor are mixed in the chamber, allowing the metal-organic precursor and the second precursor to react and form a reaction product.Without limiting the mechanism, function or utility of the disclosure, it is assumed that the product from the vapor phase reaction acquires a higher molecular weight and is then condensed or otherwise deposited onto the substrate.

[0052] In some embodiments, an ALD process is used to deposition the photoresist layer. During ALD, a layer is grown on a substrate by alternately exposing the substrate area to gaseous compounds (or precursors). Unlike CVD, the precursors are introduced as a series of sequential, non-overlapping pulses. In each of these pulses, the precursor molecules react with the area in a self-limiting manner, such that the reaction ends once all reactive sites on the area are consumed. Consequently, the maximum amount of material deposited after a single exposure to all precursors on the area (a so-called ALD cycle) is determined by the nature of the precursor-area interaction.

[0053] In one embodiment of an ALD process, a metal-organic precursor is pulsed to deposit the metal-containing precursor onto the substrate surface in a first half-reaction. In some embodiments, the metal-organic precursor reacts with a suitable underlying species (e.g., OH or NH functionality on the substrate surface) to form a new self-saturating surface. Excess, unused reactants and reaction byproducts are removed, in some embodiments by evacuation pumping and / or by passing an inert purge gas. Then, in some embodiments, a second precursor, such as water or ammonia (NH3), is pulsed into the deposition chamber. The water or NH3 reacts with the metal-organic precursor on the substrate to yield a photoresist as the reaction product on the substrate surface.The second precursor also forms self-saturating bonds with the underlying reactive species to provide a further self-limiting and self-saturating second half-reaction. In some embodiments, a second rinsing step is performed to remove unused reactants and reaction byproducts. The pulses of the first and second precursors alternate with rinsing steps occurring in between until a desired thickness of the photoresist layer 15 is reached.

[0054] In some embodiments, the photoresist layer 15 is formed with a thickness of about 5 nm to about 50 nm, and in other embodiments with a thickness of about 10 nm to about 30 nm. A person skilled in the art understands that additional ranges of thicknesses within the foregoing explicit ranges are considered and included in 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. The photoresist layer thicknesses are relatively uniform to facilitate processing. In some embodiments, the coating thickness varies by no more than ± 25% of the average coating thickness; in other embodiments, the photoresist layer thickness varies by no more than ± 10% of the average photoresist layer thickness. In some embodiments, such as…For coatings with high uniformity on larger substrates, the evaluation of the photoresist layer uniformity can be assessed with a 1-centimeter edge exclusion; that is, the uniformity of the layer is not evaluated for sections of the coating within 1 centimeter of the edge. A person skilled in the art understands that additional areas within the foregoing explicit scopes are considered and included in this disclosure.

[0055] In some embodiments, the first and second compounds or the first and second precursors are introduced into the deposition chamber with a carrier gas. The carrier gas, purge gas, deposition gas, or other process gas may contain nitrogen, hydrogen, argon, neon, helium, or combinations thereof.

[0056] A lacquer layer deposition device 200 according to some embodiments of the disclosure is in Fig. Figure 8 shows that in some embodiments, the deposition device 200 is an ALD or CVD device. The deposition device 200 includes a vacuum chamber 205. A substrate support platform 210 in the vacuum chamber 205 supports a substrate 10, such as a silicon wafer. In some embodiments, the substrate support platform 210 includes a heating device. In some embodiments, a gas supply 220 for the first precursor or compound and a carrier / purge gas supply 225 are connected via a gas line 235 to an inlet 230 in the chamber, and a gas supply 240 for the second precursor or compound and a carrier / purge gas supply 225 are connected via another gas line 235' to another inlet 230' in the chamber. The chamber is evacuated and excess reactants and reaction by-products are removed by a vacuum pump 245 via an outlet 250 and an outlet line 255.In some embodiments, the flow rate or pulses of precursor gases and carrier / purge gases, the evacuation of excess reactants and reaction by-products, the pressure in the vacuum chamber 205 and the temperature of the vacuum chamber 205 or the wafer carrier platform 210 are controlled by a controller 260 configured to control each of these parameters.

[0057] In some embodiments, the organometallic compound includes tin (Sn), antimony (Sb), bismuth (Bi), indium (In), and / or tellurium (Te) as a metal component; however, the disclosure is not limited to these metals. In other embodiments, it includes 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 as additional suitable metals. The additional metals may be used alternatively or in addition to Sn, Sb, Bi, In, and / or Te.

[0058] The specific metal used can significantly influence radiation absorption. Therefore, the metal component can be selected based on the desired radiation and absorption cross-section. Tin, antimony, bismuth, tellurium, and indium offer strong absorption of extreme ultraviolet light at 13.5 nm. Hafnium provides good absorption of electron beams and extreme ultraviolet radiation. Metal compositions containing titanium, vanadium, molybdenum, or tungsten exhibit strong absorption at longer wavelengths, for example, to provide sensitivity to ultraviolet light with a wavelength of 248 nm.

[0059] In some embodiments, the ALD or CVD deposition parameters are varied during the deposition process to form a density gradient photoresist layer. In some embodiments, the density gradient photoresist layer reduces defects, such as deposits and bridging, and improves line width roughness (LWR) and line edge roughness (LER).

[0060] Fig. Figure 9A shows a reaction to which the components of the photoresist composition are subjected as a result of exposure to actinic radiation and heating, according to an embodiment of the disclosure. Fig. Figure 9A shows an exemplary chemical structure of the photoresist layer (PR) at various stages of the photoresist structuring process according to embodiments of the disclosure. As in Fig. As shown in Figure 9A, the photoresist composition includes a metal-organic compound, e.g., SnX2R2, and a second compound, e.g., ammonia (NH3). When the metal-organic compound and the ammonia are combined, the metal-organic compound reacts with some of the ammonia in the vapor phase to form a reaction product with amine groups attached to the metal (Sn) of the metal-organic compound. The amine groups in the deposited photoresist layer exhibit hydrogen bonds, which can significantly increase the boiling point of the deposited photoresist layer and prevent outgassing of the metal-containing photoresist material, thus preventing contamination of the deposition chamber and semiconductor device processing equipment by the metal in the metal-containing photoresist. Furthermore, the hydrogen bonds of the amine groups can control the effect of humidity on the quality of the photoresist layer.

[0061] Upon subsequent exposure to extreme ultraviolet radiation using a mask, the organometallic compound absorbs the radiation, and one or more organic R groups are cleaved from the compound to form an amino-metal compound in the exposed areas. Then, when post-exposure bake-off (PEB) is performed, the amino-metal compounds crosslink in some embodiments via the amine groups, as shown in Fig. Figure 9A shows that in some embodiments, partial crosslinking of the amino-metal compounds occurs as a result of exposure to extreme ultraviolet radiation. The selectively exposed photoresist is then developed, and the crosslinked, radiation-exposed pattern remains above the substrate, while the radiation-unexposed areas are removed during development.

[0062] Fig. Figure 9B shows a reaction to which the components of the photoresist composition are subjected as a result of exposure to actinic radiation and heating, according to an embodiment of the disclosure. Fig. Figure 9B shows an exemplary chemical structure of the photoresist layer (PR) at various stages of the photoresist structuring process according to embodiments of the disclosure. As in Fig. As shown in Figure 9B, the photoresist composition includes an organometallic compound, e.g., SnX3R, and a second compound, e.g., water (H2O). When the organometallic compound and the water (the vapor) are combined in a CVD process, the organometallic compound reacts with a portion of the water in the vapor phase to form a reaction product with hydroxyl groups (-OH) attached to the metal (Sn) of the organometallic compound by substituting X with -OH. The reaction product is then subjected to a CVD process to form a film over the substrate, in which the hydroxyl-metal compounds are cross-linked by the hydroxyl groups in some embodiments.

[0063] The cross-linked structure in the deposited photoresist layer can significantly increase the boiling point of the deposited photoresist layer and prevent outgassing of metal-containing photoresist material, thereby preventing contamination of the deposition chamber and the processing equipment for semiconductor devices by the metal in the metal-containing photoresist.

[0064] Upon subsequent exposure to extreme ultraviolet radiation using a mask, the metal-organic compound absorbs the radiation, and one or more organic R groups are cleaved from the compound to form a cross-linked metal oxide compound in the exposed areas. In some embodiments, hydrogen remains after the organic R groups are cleaved. Then, when post-exposure bake-off (PEB) is performed, the cross-linked metal oxide compounds, in some embodiments, further cross-link through the hydrogen and oxygen, as shown in Fig. Figure 9B shows that in some embodiments, partial crosslinking occurs as a result of exposure to extreme ultraviolet radiation. The selectively exposed photoresist is then developed, and the crosslinked, radiation-exposed pattern remains above the substrate, while the radiation-unexposed areas are removed during development.

[0065] In some embodiments, a layer to be structured (target layer) 60 is arranged above the substrate before the formation of the photoresist layer, as in Fig. Figure 10 shows the following. In some embodiments, the layer 60 to be structured is a metallization layer or a dielectric layer, such as a hard mask layer, a layer with an interlayer dielectric, or a passivation layer, arranged over a metallization layer. In other embodiments, the target layer is a bottom antireflective coating (BARC) layer consisting of an organic polymer. In embodiments in which the layer 60 to be structured is a metallization layer, the layer 60 to be structured is formed from a conductive material using metallization processes and metal deposition techniques, including chemical vapor deposition, atomic layer deposition, and physical vapor deposition (sputtering).If the layer 60 to be structured is a dielectric layer, the layer 60 to be structured is likewise formed by techniques for the formation of dielectric layers, including thermal oxidation, chemical vapor deposition, atomic layer deposition and physical vapor deposition.

[0066] The photoresist layer 50 is then selectively exposed to actinic radiation 45 to form exposed areas 50 and unexposed areas 52 in the photoresist layer, as shown in the Fig. 11A and Fig. 11B shown and herein with reference to the Fig. 3A and Fig. 3B described. As explained herein, in some embodiments the photoresist is a negative photoresist.

[0067] The unexposed photoresist areas 52 are exposed by dispensing a developer 57 from a dispenser 62, as in Fig. 12A shown, or by a dry development process, as in Fig. 12B shown, developed to form a photoresist pattern 55, as in Fig. 13 shown. The development process is similar to that described herein with reference to the Fig. 4A, Fig. 4B and Fig. 5 is explained.

[0068] Then, as in Fig. As shown in Figure 14, the pattern 55 in the photoresist layer 15 is transferred to the layer 60 to be structured using an etching process, and the photoresist layer is removed, as described in Figure 14. Fig. 6 explains how to form a pattern 55" in layer 60 to be structured.

[0069] The Fig. Figures 15A-15J show various stages of a sequential fabrication process of a semiconductor device according to embodiments of the present disclosure. It is understood that additional processes may occur before, during, and after the stages described in the Fig. The processes shown in Figures 15A-15J can be provided, and some of the operations described below can be replaced or eliminated for additional embodiments of the method. The sequence of the process steps / processes can be interchangeable. Materials, configuration, dimensions, and / or processes that differ from those shown in the Fig. The embodiments described in 1-14 above are identical or similar to those described above and may be used in the following embodiments and a detailed explanation thereof is unnecessary.

[0070] The Fig. Figures 15A-15F illustrate a process in the case of a positive developer. As in Fig. As shown in Figure 15A, a target layer 12 to be structured is formed over a substrate 10. In some embodiments, the target layer 12 is a conductive layer, such as a metal or metallic layer (Ti, TiN, Ta, TaN, W, Cu, Al, Co, Ni, Mo, Ru or an alloy thereof, or any suitable conductive material used in semiconductor manufacturing), or a semiconductor layer (amorphous, polycrystalline, or crystalline Si, SiGe, or Ge, doped or undoped, or any suitable semiconductor material used in semiconductor manufacturing), or a dielectric layer, such as silicon oxide, silicon nitride, SiON, SiOC, SiOCN, SiCN, hafnium oxide, aluminum oxide, or any suitable dielectric material used in semiconductor manufacturing. In some embodiments, a mask layer 14 is formed over the target layer 12.In some embodiments, the mask layer 14 includes a dielectric material, a semiconductor material, or a conductive material with a sufficiently higher etch resistance than the target layer 12. In some embodiments, the mask layer 14 is an organic bottom antireflective coating (BARC). Furthermore, a metal-containing lacquer layer 15 is formed over the mask layer 14, as described above.

[0071] Then, as in Fig. Figure 15B shows an exposure process on the metal-containing lacquer layer 15 by EUV or DUV radiation, which is reflected by or passes through a photomask with circuit patterns. Then, as shown in Fig. As shown in 15C, the exposed metallic lacquer layer 15 is developed and removed by a wet developer or a dry developer. Next, as shown in Fig. Figure 15D shows the mask layer 14 being structured by using the structured metallic layer 15 as an etching mask. In some embodiments, the metal-containing lacquer layer 15 is then removed using a suitable wet or dry etching agent, as shown in Fig. 15E is shown. Then the target layer 12 is structured using the structured mask layer 14 as an etching mask, and the mask layer 14 is removed as shown in Fig. Figure 15F shows that in some embodiments the target layer 12 is structured without removing the metal-containing lacquer layer 15. In some embodiments the structured mask layer 14 is not removed after structuring the target layer 12.

[0072] The Fig. Figures 15G-15J illustrate a process in the case of a negative developer. As in Fig. As shown in Figure 15G, the unexposed areas of the metal-containing lacquer layer 15 are developed and removed by a wet or dry developer. The processes in the Fig. 15H, Fig. 15I and Fig. 15 years are the same as in Fig. 15D, Fig. 15E and Fig. 15F.

[0073] Other embodiments include other processes before, during, or after the processes described above. In some embodiments, the disclosed methods include the formation of Fin field-effect transistor (FinFET) structures. In some embodiments, a plurality of active lamellae are formed on the semiconductor substrate. Such embodiments further include etching the substrate through the openings of a structured hard mask to form trenches in the substrate; filling the trenches with a dielectric material; performing a chemical-mechanical polishing (CMP) process to form shallow trench isolation (STI) features; and epitaxially growing or deepening the STI features to form lamella-like active regions. In some embodiments, one or more gate electrodes are formed on the substrate.Some embodiments include the formation of gate spacers, doped source / drain regions, contacts for gate / source / drain functions, etc. In other embodiments, a target pattern is formed as metal conductors in a multilayer interconnect structure. The metal conductors can be formed, for example, in a layer of the substrate containing an interlayer dielectric (ILD) that has been etched to form a variety of trenches. The trenches can be filled with a conductive material, such as a metal; and the conductive material can be polished using a process such as chemical-mechanical planarization (CMP) to expose the structured ILD layer, thereby forming the metal conductors within the ILD layer.The above descriptions are non-limiting examples of components / structures that can be manufactured and / or improved using the method described herein.

[0074] In some embodiments, active components such as diodes, field-effect transistors (FETs), metal-oxide semiconductor field-effect transistors (MOSFETs), complementary metal-oxide semiconductor (CMOS) transistors, bipolar transistors, high-voltage transistors, high-frequency transistors, FinFETs, other three-dimensional (3D) FETs, metal-oxide semiconductor field-effect transistors (MOSFETs), complementary metal-oxide semiconductor (CMOS) transistors, bipolar transistors, high-voltage transistors, high-frequency transistors, other memory cells and combinations thereof are formed according to embodiments of the disclosure.

[0075] It is understood that not all advantages have necessarily been discussed here, that no particular advantage is required for all embodiments or examples, and that other embodiments or examples may offer other advantages.

[0076] Semiconductor formation and resist structuring processes according to the present disclosure provide improved utilization efficiency of the resist material and reduced use of potentially toxic organic solvents compared to solvent-based resists. Embodiments of the disclosure provide organotin precursors with lower Sn-C BDE, resulting in photoresist films with higher EUV sensitivity at a lower EUV dose. Embodiments of the present disclosure provide a more cost-effective EUV structuring process. Embodiments of the disclosure further provide a uniform photoresist film that is deposited on the surface of a semiconductor substrate.Furthermore, toxic organic solvents can be essentially eliminated from the photoresist structuring process because the photoresist is solvent-free and dry development is performed in some embodiments without the use of a solvent-based developer. In some embodiments, contamination of the deposition chamber and semiconductor substrate handling equipment by metals in metal-containing photoresists is prevented. Problems with the moisture sensitivity of the photoresist are prevented by methods according to embodiments of the disclosure. Improved pattern resolution is provided by embodiments of the present disclosure. Embodiments of the disclosure provide improved linewidth roughness and improved discrimination between exposed and unexposed areas of the photoresist.Furthermore, improved semiconductor device manufacturing efficiency is provided by the one-pot deposition processes according to embodiments of the disclosure. The metal-containing photoresist enables the formation of patterns with dimensions ranging from approximately 5 nm to approximately 40 nm, exhibiting low linewidth roughness (LWR) and high etch selectivity. In some embodiments, the LWR is improved by approximately 20% compared to a polymer-based photoresist.

[0077] According to one aspect of the present disclosure, in a process for fabricating a semiconductor device, a photoresist layer is formed over a target layer to be structured by combining a first precursor and a second precursor in a vapor state to form a photoresist material. The first precursor is a metal-organic material with the formula: M a R b X c, where M is one or more selected from the group consisting of Sn, Bi, Sb, In, and Te, R is an alkyl group substituted by different electron-donating groups (EDG) or electron-withdrawing groups (EWG), X is a halide or sulfonate group, and 1 ≤ a ≤ 2, b ≥ 1, c ≥ 1, and b + c ≤ 4, and the second precursor is one or more selected from the group consisting of water, an amine, a borane, and a phosphine. The photoresist material is deposited over the target layer to be patterned. 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 or more of the preceding or following embodiments, R is a C1-C20 alkyl group, including all isomers of C1-C20 alkyl groups, substituted with an electron-donating group selected from one or more of the following: -O. - -NH2, -NHR1, -NR12, -OH, -OR1, -NHCOR1, -SH, -SRI, phenyl group and -(C=O)O-, wherein R1 = C1-C4 groups or phenyl groups. In one or more of the preceding or following embodiments, R is a C1-C20 alkyl group, including all isomers of C1-C20 alkyl groups, substituted with an electron-withdrawing group selected from one or more of -I, -Cl, -Br, -F, -NR23. +-NO2, -SO3H, -SO2R2, -CN, -CHO, -COR2, -CO2H, -CO2R2, -CONH2, -CONHR2 and -CONR22, wherein R2 = C1-C4 groups or phenyl groups. In one or more of the preceding or following embodiments, R is one or more C1-C4 alkyl groups substituted with a phenyl group, -NH2, -NHR3, -NR32, -OH, -OR3, wherein R3 = C1-C3 alkyl group or a phenyl group. In one or more of the preceding or following embodiments, R is one or more C1-C4 alkyl groups substituted at the α-C position by one or two phenyl groups, -NH2, -NHR4, -NR42 or -OR4, wherein R4 = C1-C3 alkyl group. In one or more of the preceding or following embodiments, the actinic radiation is extreme ultraviolet radiation.In one or more of the preceding or following embodiments, after selective exposure of the photoresist layer with actinic radiation to form a latent pattern, and before developing the latent pattern, post-exposure baking of the photoresist layer is performed. In one or more of the preceding or following embodiments, the photoresist material is deposited over the target layer to be patterned by atomic layer deposition (ALD) or chemical vapor deposition (CVD). In one or more of the preceding or following embodiments, the first precursor is a dimer linked by NH₃ or O₂. In one or more of the preceding or following embodiments, after selective exposure of the photoresist layer with actinic radiation to form a latent pattern, and before developing the latent pattern, the photoresist layer is heated to a temperature in the range of 150 °C to 230 °C or 100 °C to 200 °C.In one or more of the preceding or following embodiments, the developer is a dry developer. In one or more of the preceding or following embodiments, the photoresist layer is heated to a temperature in the range of 40 °C to 120 °C before selective exposure of the photoresist layer with actinic radiation to form a latent pattern.

[0078] According to another aspect of the present disclosure, in a process for fabricating a semiconductor device, a photoresist layer is formed over a target layer to be structured by combining a first precursor and a second precursor in a vapor state to form a photoresist material. The first precursor is a metal-organic material with the formula: M a R b X c, where M is one or more selected from the group consisting of Sn, Bi, Sb, In, and Te, R is an alkyl group substituted by different electron-donating groups (EDG) or electron-withdrawing groups (EWG), X is a halide or sulfonate group, and a = 1 or 2, b = 2, and c = 2, and the second precursor is one or more selected from the group consisting of water, an amine, a borane, and a phosphine. The photoresist material is deposited over the target layer to be patterned. 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 or more of the preceding or following embodiments, a = 1.In one or more of the preceding or following embodiments, a=2 and the first precursor is a metal-organic material with the formula MR2X2-NH-MR2X2. In one or more of the preceding or following embodiments, the second precursor is ammonia.

[0079] According to another aspect of the present disclosure, in a process for fabricating a semiconductor device, a photoresist layer is formed over a target layer to be structured by combining a first precursor and a second precursor in a vapor state to form a photoresist material. The first precursor is a metal-organic material with the formula: M a R b X c, where M is one or more selected from the group consisting of Sn, Bi, Sb, In, and Te, R is an alkyl group substituted by different electron-donating groups (EDG) or electron-withdrawing groups (EWG), X is a halide or sulfonate group, and a = 1 or 2, b = 1, and c = 3, and the second precursor is one or more selected from the group consisting of water, an amine, a borane, and a phosphine. The photoresist material is deposited over the target layer to be patterned. 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 or more of the preceding or following embodiments, a = 1.In one or more of the preceding or following embodiments, a=2 and the first precursor is a metal-organic material with the formula MRX3-O-MRX3. In one or more of the preceding or following embodiments, the second precursor is water vapor.

[0080] The foregoing outlines features of several embodiments or examples so that the person skilled in the art can better understand the aspects of the present disclosure. The person skilled in the art should be aware that they can readily use the present disclosure as a basis for designing or modifying other processes and structures to achieve the same purposes and / or the same advantages as the embodiments or examples presented herein. The person skilled in the art should also recognize that such equivalent designs do not deviate from the spirit and scope of the present disclosure and that they can make various changes, substitutions, and modifications to them without deviating from the spirit and scope of the present disclosure. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] US 63047350

[0001] US 63 / 049956

[0001]

Claims

[1] A method of manufacturing a semiconductor device, comprising: Forming a photoresist layer over a target layer to be structured, wherein forming the photoresist layer comprises: Combining a first precursor and a second precursor in a vapor state to form a photoresist material, wherein the first precursor is a metal-organic material having the following formula: M a R b X c where M is one or more selected from the group consisting of Sn, Bi, Sb, In and Te, R is an alkyl group substituted by one or more electron-donating groups (EDG) or electron-withdrawing groups (EWG), X is a halide or sulfonate group, and 1 ≤ a ≤ 2, b ≥ 1, c ≥ 1 and b + c ≤ 4, and the second precursor is one or more selected from the group consisting of water, an amine, a borane and a phosphine; and Depositing the photoresist material over the target layer to be structured; selectively exposing the photoresist layer to actinic radiation to form a latent pattern; and Developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern. [2] The process of claim 1, wherein R is a C1-C20 alkyl group, including all isomers of C1-C20 alkyl groups, substituted with an electron-donating group selected from one or more of the following: -O - -NH2, -NHR1, -NR12, -OH, -OR1, -NHCOR1, -SH, -SR1, phenyl group and -(C=O)O-, where R1 = C1-C4 groups or phenyl groups. [3] The process of claim 1, wherein R is a C1-C20 alkyl group, including all isomers of C1-C20 alkyl groups, substituted with an electron withdrawing group selected from one or more of -I, -Cl, -Br, -F, -NR23 + , -NO2, -SO3H, - SO2R2, -CN, -CHO, -COR2, -CO2H, -CO2R2, -CONH2, -CONHR2 and -CONR22, where R2 = C1-C4 groups or phenyl groups. [4] The process according to claim 1, wherein R is one or more C1-C4 alkyl groups substituted with a phenyl group, -NH2, -NHR3, -NR32, -OH, -OR3, where R3 = C1-C3 alkyl group or a phenyl group. [5] A process according to claim 1, wherein R is one or more C1-C4 alkyl groups substituted at the α-C position by one or two phenyl groups, -NH2, -NHR4, -NR42 or -OR4, where R4 = C1-C3 alkyl group. [6] A method according to any one of the preceding claims, wherein the actinic radiation is extreme ultraviolet radiation. [7] A method according to any one of the preceding claims, further comprising, after selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before developing the latent pattern, annealing the photoresist layer after exposure. [8] A method according to any one of the preceding claims, wherein the photoresist material is deposited by atomic layer deposition (ALD) or chemical vapor deposition (CVD) over the target layer to be patterned. [9] A process according to any one of the preceding claims, wherein the first precursor is a dimer linked by NH or O. [10] A method according to any one of the preceding claims, further comprising, after selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before developing the latent pattern, heating the photoresist layer at a temperature in the range of 150°C to 230°C. [11] A method according to any one of the preceding claims, wherein the developer is a dry developer. [12] A method according to any one of the preceding claims, further comprising, prior to selectively exposing the photoresist layer to actinic radiation to form a latent pattern, heating the photoresist layer at a temperature in the range of 40°C to 120°C. [13] A method of manufacturing a semiconductor device, comprising: Forming a photoresist layer over a target layer to be structured, wherein forming the photoresist layer comprises: Combining a first precursor and a second precursor in a vapor state to form a photoresist material, wherein the first precursor is a metal-organic material having the following formula: M a R b X c where M is one or more selected from the group consisting of Sn, Bi, Sb, In and Te, R is an alkyl group substituted by one or more electron-donating groups (EDG) or electron-withdrawing groups (EWG), X is a halide or sulfonate group, and a=1 or 2, b =2 and c=2, and the second precursor is one or more selected from the group consisting of water, an amine, a borane and a phosphine; and Depositing the photoresist material over the target layer to be structured; selectively exposing the photoresist layer to actinic radiation to form a latent pattern; and Developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern. [14] The method of claim 13, wherein a=1. [15] The method of claim 13, wherein a=2 and the first precursor is a metal-organic material having a formula MR2X2-NH-MR2X2. [16] A process according to any one of the preceding claims 13 to 15, wherein the second precursor is ammonia. [17] A method of manufacturing a semiconductor device, comprising: Forming a photoresist layer over a target layer to be structured, wherein forming the photoresist layer comprises: Combining a first precursor and a second precursor in a vapor state to form a photoresist material, wherein the first precursor is a metal-organic material having the following formula: M a R b X c where M includes one or more of Sn, Bi, Sb, In or Te, R is an alkyl group substituted by one or more electron-donating groups (EDG) or electron-withdrawing groups (EWG), X is a halide or sulfonate group, and a=1 or 2, b =1 and c=3, and the second precursor includes one or more of water, an amine, a borane, or a phosphine; and Depositing the photoresist material over the target layer to be structured; selectively exposing the photoresist layer to actinic radiation to form a latent pattern; and Developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern. [18] The method of claim 17, wherein a=1. [19] The method of claim 17, wherein a=2 and the first precursor is a metal-organic material having a formula MRX3-O-MRX3. [20] A process according to any one of the preceding claims 17 to 19, wherein the second precursor is water vapor.