MANUFACTURING METHOD OF A SEMICONDUCTOR DEVICE

Abstract

A method for producing a semiconductor device, comprising: forming a photoresist layer over a substrate, comprising: combining a first precursor and a second precursor in a vapor state to form a photoresist material, wherein the first precursor has the following formula: MaRbXc, where 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 and Lu, where R is a substituted or unsubstituted alkyl, alkenyl or carboxylate group, where X is a halide or sulfonate group, and where 1 ≤ a ≤ 2, b ≥ 1, c ≥ 1, and b + c ≤ 5, and where the second precursor is at least one of an amine, a borane and a phosphine; and deposition of the photoresist material onto the substrate; selective exposure of the photoresist layer with actinic radiation to form a latent structure;and developing the latent structure by applying a developer to the selectively exposed photoresist layer to form a structure.;

Description

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[0001] This application claims priority over the preliminary US patent application 63 / 002,247, filed on March 30, 2020, and the preliminary US patent application 63 / 025,957, filed on May 15, 2020, the entire contents of which are hereby incorporated by reference into the present text. BACKGROUND

[0002] As consumer demand has driven the miniaturization of consumer electronics, the individual components of these devices have inevitably become smaller as well. Semiconductor devices, which are a key component of devices such as mobile phones, tablets, and the like, have had to become increasingly smaller, which in turn has led to the individual components (e.g., transistors, resistors, capacitors, etc.) within the semiconductor devices also becoming 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 energy that has itself been patterned. This exposure modifies the chemical and physical properties of the exposed regions of the photosensitive material. This modification, along with the lack of modification in regions of the photosensitive material that were not exposed, can be used to remove a region without removing the others.

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

[0005] The present disclosure is best understood with reference to the following detailed description in conjunction with the accompanying figures. It should be noted that, in accordance with industry practice, various structural elements are not drawn to scale and are for illustrative purposes only. The dimensions of the various structural elements may, in fact, be enlarged or reduced as necessary for the sake of clarity in this discussion. Fig. Figure 1 illustrates a process flow for manufacturing a semiconductor device according to embodiments of the disclosure. Fig. Figure 2 shows a process stage of a sequential operation according to an embodiment of the disclosure. Fig. 3A and Fig. Figure 3B shows a process stage of a sequential operation according to an embodiment of the disclosure. Fig. 4A and Fig. Figure 4B shows a process stage of a sequential operation according to an embodiment of the disclosure. Fig. Figure 5 shows a process stage of a sequential operation according to an embodiment of the disclosure. Fig. Figure 6 shows a process stage of a sequential operation according to an embodiment of the disclosure. Fig. Figure 7 shows organometallic precursors according to embodiments of the disclosure. Fig. Figure 8 shows a device for depositing photoresist according to some embodiments of the disclosure. Fig. Figure 9 shows a reaction that the photoresist layer undergoes as a result of the action of actinic radiation and heating according to an embodiment of the disclosure. Fig. Figure 10 shows a process stage of a sequential operation according to an embodiment of the disclosure. Fig. 11-A and Fig. Figure 11B shows a process stage of a sequential operation according to an embodiment of the disclosure. Fig. 12A and Fig. Figure 12B shows a process stage of a sequential operation according to an embodiment of the disclosure. Fig. Figure 13 shows a process stage of a sequential operation according to an embodiment of the disclosure. Fig. Figure 14 shows a process stage of a sequential operation according to an embodiment of the disclosure. Fig. Figure 15 shows a process stage of a sequential operation according to an embodiment of the disclosure. Fig. Figure 16A shows a process stage of a sequential operation according to an embodiment of the disclosure, and Fig. Figure 16B shows a reaction that the photoresist layer undergoes during the processing stage. Fig. Figure 17 shows a process stage of a sequential operation according to an embodiment of the disclosure. Fig. Figure 18 shows a process stage of a sequential operation according to an embodiment of the disclosure. Fig. Figure 19A shows a process stage of a sequential operation according to an embodiment of the disclosure. Fig. 19B shows a detailed view of Fig. 19A. Fig. 19C shows a reaction that the organometallic precursor undergoes. DETAILED DESCRIPTION

[0006] It is understood that the following disclosure provides many different embodiments or examples for implementing various features of the disclosure. Specific embodiments or examples of components and arrangements are described below to simplify the present disclosure. These are, of course, only examples and are not intended to be limiting. For example, the dimensions of elements are not limited to the disclosed range or values ​​but may depend on the process conditions and / or desired properties of the device.Furthermore, the formation of a first structural element above or on top of a second structural element in the following description may include embodiments in which the first and second structural elements are in direct contact, and may also include embodiments in which additional structural elements may be formed between the first and second structural elements, so that the first and second structural elements may not be in direct contact. Various features may be arbitrarily drawn to different scales for the sake of simplicity and clarity.

[0007] Furthermore, spatially relative terms, such as "below," "under," "lower," "above," "upper," and the like, may be used in this text to simplify the description and to describe the relationship of one element or feature to one or more other elements or features, as illustrated in the figures. These spatially relative terms are intended to encompass other orientations of the device in use or operation besides the orientation shown in the figures. The device may also be oriented differently (rotated by 90 degrees, or in other orientations), and the spatially relative descriptors used in this text may be interpreted accordingly. Additionally, the term "made of" can mean either "comprises" or "consists of."

[0008] As the semiconductor industry has advanced into the nanometer technology process node range in pursuit of higher device density, increased performance, and lower costs, challenges have arisen related to the miniaturization of semiconductor devices. Extreme ultraviolet lithography (EUVL) has been developed to create smaller structural elements in semiconductor devices and increase the device density on a semiconductor wafer. To improve EUVL, an increase in wafer exposure throughput is desirable. Wafer exposure throughput can be improved by increasing the exposure power or the resist exposure rate (sensitivity).

[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 rate. However, metal-containing photoresist layers can outgas during processing, which can lead to changes in the quality of the photoresist layer over time and the formation of impurities, thereby impairing lithographic 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 crosslinking. This uneven exposure results from a lower amount of light energy reaching the lower sections of the photoresist layer. Uneven exposure can lead to poor line width roughness (LWR), preventing the formation of a straight edge resist profile.

[0011] Because the solvents used in the formation and development of solvent-based photoresists can be toxic, a more environmentally friendly process for forming a photoresist layer and subsequent structure formation without the use of toxic solvents is desirable.

[0012] Furthermore, in a spin coating process, only 2–5% of the material applied to the substrate may be used, while the remaining 95–98% is flung off during the spin coating operation. A photoresist deposition operation with a high degree of material utilization 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, photoresist layer formation and structuring operations are desirable that 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 operation, including atomic layer deposition (ALD) or chemical vapor deposition (CVD) of the photoresist material. Photoresist layers deposited by a vapor deposition operation according to embodiments of the disclosure provide photoresist layers that exhibit a controllable layer thickness and high film uniformity and density over a large deposition area. Furthermore, embodiments of the disclosure include the formation of layers from solvent-free photoresist, thereby providing a more environmentally friendly process.Furthermore, the photoresist deposition operation is a one-pot process (i.e., it is carried out in a single chamber), which increases manufacturing efficiency and limits or prevents metal contamination of the process chambers.

[0016] Fig. 1 illustrates a process flow 100 for manufacturing a semiconductor device according to embodiments of the disclosure. In some embodiments, in operation S110 a resist on a surface of a layer or substrate to be structured 10 coated to create a resist layer 15 to form, as in Fig. 2 shown. In some embodiments, the resist is a metal-containing photoresist formed by CVD or ALD. In some embodiments, the resist layer 15 after their initial warming operation S120The resist layer is subjected to a temperature of approximately 40 °C to approximately 120 °C for about 10 seconds to about 10 minutes.

[0017] After the optional initial warming operation S120 or the resist deposition operation S110 The photoresist layer 15 in operation S130 selective actinic radiation 45 / 97 suspended (see Fig. 3A and Fig. 3B). In some embodiments, the photoresist layer 15 The photoresist layer is selectively or structurally exposed to ultraviolet radiation. In some embodiments, the ultraviolet radiation is deep ultraviolet (DUV) radiation. In some embodiments, the ultraviolet radiation is extreme ultraviolet (EUV) radiation. In some embodiments, the photoresist layer is selectively or structurally exposed to an electron beam.

[0018] As in Fig. As shown in 3A, the exposure radiation passes 45 in some embodiments a photomask 30 , before they form the photoresist layer 15 irradiated. In some embodiments, the photomask has a structure that is located in the photoresist layer. 15 The structure is to be replicated. In some embodiments, the structure is represented by an opaque structure. 35 on the photomask substrate 40 formed. The opaque structure 35 can be formed from a material opaque to ultraviolet radiation, such as chromium, while the photomask substrate 40 is formed from a material that is permeable to ultraviolet radiation, such as quartz glass.

[0019] In some embodiments, the photoresist layer is selectively or structure-wise exposed. 15 to create exposed regions 50 and unexposed regions 52performed using extreme ultraviolet lithography. In some embodiments of the extreme ultraviolet lithography operation, a reflective photomask is used. 65 used to form the structured exposure light, as in Fig. Shown in 3B. The reflective photomask 65 includes a glass substrate 70 with low thermal expansion, on which a reflective multilayer 75 It is formed from Si and Mo. A cap layer 80 and an absorber layer 85 are applied to the reflective multilayer 75 formed. On the back of the substrate 70 A conductive layer on the back is formed with low thermal expansion. 90 formed. Extreme ultraviolet radiation 95 The light is directed at an angle of incidence of approximately 6° onto the reflecting photomask. 65 directed. A part 97 The extreme ultraviolet radiation is blocked by the Si / Mo multilayer.75 in the direction of the photoresist-coated substrate 10 reflected, while the portion of the extreme ultraviolet radiation that hits the absorber layer 85 The light is absorbed by the photomask. In some embodiments, additional optics, such as mirrors, are placed between the reflective photomask and the light source. 65 and arranged on the photoresist-coated substrate.

[0020] In some embodiments, the irradiation is carried out by placing the photoresist-coated substrate into a photolithography tool. The photolithography tool includes a photomask. 30 / 65 , an optic, an exposure radiation source, to project the radiation 45 / 97 to provide for exposure, and a movable table to support and move the substrate under the exposure radiation.

[0021] In some embodiments, optics (not shown) are used in the photolithography tool to expand, reflect, or otherwise control the radiation before or after the radiation is emitted. 45 / 97 through the photomask 30 / 65 is structured. In some embodiments, the optics comprise one or more lenses, mirrors, filters, and combinations thereof to focus the radiation. 45 / 97 to steer along their 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 selected from the group consisting of a mercury vapor lamp, a xenon lamp, a carbon arc lamp, a KrF excimer laser light (wavelength of 248 nm), an ArF excimer laser light (wavelength of 193 nm), an F2 excimer laser light (wavelength of 157 nm), or a CO2 laser-excited Sn plasma (extreme ultraviolet, 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 over the exposure time. Suitable radiation fluences range from approximately 1 mJ / cm² in some embodiments.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 of about 3 mJ / cm² 2 up to about 50 mJ / cm² 2 The average person will recognize that further areas of radiation influence are to be considered within the above-mentioned explicit areas and are within the scope of this disclosure.

[0024] In some embodiments, selective or structure-wise exposure is achieved using a scanning electron beam. In 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. 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. Near-corrected beam doses at 30 kV range from 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 2The average person can calculate corresponding doses at other beam energies based on the teachings described in this text and recognizes that further areas of electron beam properties are to be considered within the explicit areas described above and are within the scope of this disclosure.

[0025] The region of the photoresist layer that is exposed to radiation 50 When exposed to chemicals, the body undergoes a chemical reaction, which increases its readiness to participate in a subsequent developmental operation. S150 to remove changes. In some embodiments, the section of the photoresist layer exposed to radiation passes through 50 is exposed to a reaction, causing the exposed section to change during the development operation. S150 which is easier to remove. In other embodiments, the section of the photoresist layer exposed to radiation passes through 50is exposed to a reaction that protects the exposed section against removal during the development operation S150 makes you resistant.

[0026] Next, the photoresist layer will be applied. 15 in operation S140 It is subjected to a second heating or baking process after exposure (post-exposure bake, PEB). In some embodiments, the photoresist layer is 15 The material is heated to a temperature of approximately 50 °C to approximately 250 °C for approximately 20 seconds to approximately 120 seconds. In some embodiments, firing after exposure 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 firing operation causes S140 after exposure, the reaction product of the first compound or first precursor and the second compound or second precursor is cross-linked.

[0027] The selectively exposed photoresist layer is then used in surgery. S150 developed. In some embodiments, the photoresist layer 15 by applying a solvent-based developer 57 developed onto the selectively exposed photoresist layer. As in Fig. As shown in 4A, a liquid developer will be used. 57 from an output device 62 to the photoresist layer 15 applied. In some embodiments, the exposed sections pass through 50 of the photoresist a crosslinking reaction as a result of exposure to actinic radiation or burning after exposure, and the non-exposed section of the photoresist layer 52 is provided by the developer 57 removed, creating a structure of openings 55 in the photoresist layer 15 is formed to form the substrate 20 to uncover, as in Fig. 5 shown.

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

[0029] In some embodiments, the developer 57 by means of a spin coating process onto the photoresist layer 15 applied during the spin-on application process. 57 from above onto the photoresist layer 15applied while the photoresist-coated substrate is rotated, as in Fig. 4A is shown. In some embodiments, the developer 57 supplied at a rate between approximately 5 ml / min and approximately 800 ml / min, while the photoresist-coated substrate 10 It is rotated at a speed between approximately 100 rpm and approximately 2000 rpm. In some embodiments, the developer operates at a temperature between approximately 10 °C and approximately 80 °C. The development process takes between approximately 30 seconds and approximately 10 minutes in some embodiments.

[0030] In some embodiments, the developer 57an organic solvent. The organic solvent may 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] The spin-on process is indeed a specific and suitable method for developing the photoresist layer. 15after exposure; however, this is only for illustrative purposes and does not restrict the embodiment. Rather, any suitable development operations can be used alternatively, including immersion, puddle, and spray processes. All such development operations are included within the scope of the embodiments.

[0032] In some embodiments, a dry developer is used. 105 on the selectively exposed photoresist layer 15 agitated, as in Fig. 4B shown. In some embodiments, the dry developer 105 a plasma or a chemical vapor, and the dry development operation S150Dry development is a plasma etching or chemical etching operation. It exploits differences in composition, degree of crosslinking, and film density to selectively remove desired portions of the resist. In some embodiments, dry development processes employ either a gentle plasma (high pressure, low power) or a thermal process in a heated vacuum chamber while a dry development chemical, such as BCl3, BF3, or another Lewis acid, is introduced in vapor form. In some embodiments, the BCl3 removes the unexposed material, leaving behind a structure 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 for about 1 to about 3000 seconds at a pressure in the range of about 5 mTorr to about 20 mTorr, at a power 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.

[0034] After the development operation, additional processing is performed while the structured photoresist layer is being built up. 50 in its place. For example, in some embodiments, an etching operation is performed using dry or wet sets to alter the structure of the photoresist layer. 50 on the underlying substrate 10 to transfer, thereby creating recesses55' be formed, as in Fig. 6 shown. The substrate 10 has a different etching resistance than the photoresist layer 15 In some embodiments, the etchant is for the substrate 10 more selective than for the photoresist layer 15 .

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

[0036] In some embodiments, the substrate contains 10 a single-crystal semiconductor layer on at least its surface section. The substrate 10It may contain a single-crystal semiconductor material, such as Si, Ge, SiGe, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs, GaSbP, GaAsSb and InP, but is not limited to these. In some embodiments, the substrate is 10 a silicon layer of an SOI substrate (silicon on insulator substrate). In certain embodiments, the substrate is 10 Made from crystalline Si.

[0037] The substrate 10The substrate can have one or more buffer layers (not shown) in its surface region. These 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. In one embodiment, the silicon-germanium buffer layer (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 bottom buffer layer to 70 atomic percent for the top buffer layer.

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

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

[0040] The photoresist layer 15A photoresist layer is a light-sensitive layer that is structured by exposure to actinic radiation. Typically, the chemical properties of the photoresist regions exposed to the incident radiation change in a manner that depends on the type of photoresist used. Photoresist layers 15Photoresists are either positive-tone or negative-tone resists. A positive-tone resist refers to a photoresist material where, during development, the portions of the photoresist layer exposed to actinic radiation, such as UV light, are removed, while the region of the photoresist that was not (or less) exposed remains on the substrate after development. A negative-tone resist, on the other hand, refers to a photoresist material where, during development, the portions of the photoresist exposed to actinic radiation remain on the substrate, while the region of the photoresist that was not (or less) exposed is removed during development.

[0041] In some embodiments, the photoresist layer 15Prepared from a photoresist composition containing 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 an organometal with the formula: M a R b X c , as in Fig. Figure 7 shows, wherein M is selected from the group consisting of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, Lu and combinations thereof; 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, and Te. 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. X is a ligand, an ion, or another unit that is reactive with the second compound or precursor; and in some embodiments, 1 ≤ a ≤ 2, b ≥ 1, c ≥ 1, and b + c ≤ 5.In some embodiments, the alkyl, alkenyl, or carboxylate group is substituted by one or more fluorine groups. In some embodiments, the organometallic precursor is a dimer, as in [reference]. Fig. Figure 7 shows where each monomer unit is linked by an amine group. Each monomer has the formula: M a R b X c , as defined above.

[0042] In some embodiments, R is alkyl, such as C n H 2n+1 , where n ≥ 3. In some embodiments, R is fluorinated and has, for example, the formula C. n F x H ((2n+1)-x) In some embodiments, R has at least one beta-hydrogen or one beta-fluorine. In some embodiments, R is selected from the group consisting of i-propyl, n-propyl, t-butyl, i-butyl, n-butyl, sec-butyl, n-pentyl, i-pentyl, t-pentyl and sec-pentyl and combinations thereof.

[0043] In some embodiments, X is any unit that can be readily displaced by the second compound or precursor to generate an M-OH unit, such as a unit selected from the group consisting of amines, including dialkylamino and monalkylamino, alkoxy, carboxylates, halogens, and sulfonates. In some embodiments, the sulfonate group is substituted by 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 comprises a substituted or unsubstituted C1-C3 group.

[0044] In einigen Ausführungsformen umfasst der metallorganische Vorläufer oder die metallorganische Verbindung ein sec-Hexyl-tris(dimethylamino)-Zinn, t-Hexyl-tris(dimethylamino)-Zinn, i-Hexyl-tris(dimethylamino)-Zinn, n-Hexyl-tris(dimethylamino)-Zinn, sec-Pentyl-tris(dimethylamino)-Zinn, t-Pentyl-tris(dimethylamino)-Zinn, i-Pentyl-tris(dimethylamino)-Zinn, n-Pentyl-tris(dimethylamino)-Zinn, sec-Butyl-tris(dimethylamino)-Zinn t-Butyltris(dimethylamino)-Zinn, i-Butyl-tris(dimethylamino)-Zinn, n-Butyl-tris(dimethylamino)-Zinn, sec-Butyl-tris(dimethylamino)-Zinn, i-Propyl-tris(dimethylamino)-Zinn, n-Propyltris(diethylamino)-Zinn und analoge Alkyl-tris(t-butoxy)-Zinn-Verbindungen, einschließlich sec-Hexyl-tris(t-butoxy), t-Hexyl-tris(t-butoxy)-Zinn, i-Hexyl-tris(t-butoxy)-Zinn, n-Hexyltris(t-butoxy)-Zinn, sec-Pentyl-tris(t-butoxy), t-Pentyl-tris(t-butoxy)-Zinn, i-Pentyl-tris(t-butoxy)-Zinn, n-Pentyl-tris(t-butoxy)-Zinn, t-Butyl-tris(t-butoxy)-Zinn, i-Butyl-tris(butoxy)-Zinn,n-Butyl-tris(butoxy)tin, sec-Butyl-tris(butoxy)tin, i-Propyl-(tris)dimethylaminotin, or n-Propyl-tris(butoxy)tin. In some embodiments, the organometallic precursors or organometallic compounds are fluorinated. In some embodiments, the organometallic precursors or compounds have a boiling point of less than about 200 °C.

[0045] In some embodiments, the first compound or precursor contains 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.

[0046] In some embodiments, the second precursor or compound is one or more selected from the group consisting of an amine, a borane, and a phosphine. In some embodiments, the amine has the formula N p H n X m , where 0 ≤ n ≤ 3, 0 ≤ m ≤ 3, n + m = 3 when p equals 1, and n + m = 4 when p equals 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 the formula B p H n X m , where 0 ≤ n ≤ 3, 0 ≤ m ≤ 3, n + m = 3 when p equals 1, and n + m = 4 when p equals 2, and each X independently is a halogen selected from the group consisting of F, Cl, Br, and I. In some embodiments, phosphine has the formula P p H n X m, where 0 ≤ n ≤ 3, 0 ≤ m ≤ 3, n + m = 3 if p equals 1, or n + m = 4 if p equals 2, and each X independently is a halogen selected from the group consisting of F, Cl, Br and I.

[0047] 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 emission of the metallic photoresist material, thereby preventing metal contamination. The hydrogen bonds can also help prevent the effects of moisture on the quality of the photoresist layer.

[0048] In some embodiments, the operation S110The deposition of a photoresist composition is carried out by a vapor deposition operation. In some embodiments, the vapor deposition operation comprises atomic layer deposition (ALD) or chemical vapor deposition (CVD). In some embodiments, ALD comprises plasma-enhanced atomic layer deposition (PE-ALD), and CVD comprises 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 alternately into the deposition chamber (ALD chamber), that is, 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.

[0049] In some embodiments, the temperature of the deposition chamber during the deposition operation is in the range of about 30 °C to 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 operation 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 precursor and the second compound or precursor is in the range of about 100 sccm to about 1000 sccm.In some embodiments, the ratio of the flow of the metal-organic compound or metal-organic precursor to the second compound or precursor is in the range of approximately 1:1 to approximately 1:5. With operating parameters outside the aforementioned ranges, unsatisfactory photoresist layers are obtained in some embodiments. In some embodiments, the photoresist layer is formed in a single chamber (one-pot layer formation).

[0050] In a CVD process according to some embodiments of the disclosure, two or more gas streams, one of a metal-organic precursor and the other of a second precursor, are introduced into the deposition chamber of a CVD apparatus 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 double plenum showerhead. The deposition apparatus 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 usefulness of the disclosure, it is assumed that the product from the vapor phase reaction acquires a higher molecular weight and is then condensed onto the substrate or deposited in some other way.

[0051] In some embodiments, an ALD process is used to deposit the photoresist layer. During ALD, a layer is grown on a substrate by alternately exposing the substrate surface to gaseous compounds (or precursors). Unlike CVD, the precursors are introduced as a series of successive, non-overlapping pulses. In each of these pulses, the precursor molecules react with the surface in a self-limiting manner such that the reaction terminates when all reactive sites on the surface are consumed. Consequently, the maximum amount of material deposited after a single contact with all precursors on the surface (a so-called ALD cycle) is determined by the nature of the precursor-surface interaction.

[0052] In one embodiment of an ALD process, a metal-organic precursor is pulsed to introduce 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 (for example, 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 draining and / or by introducing an inert purge gas. Then, in some embodiments, a second precursor, such as ammonia (NH3), is pulsed into the deposition chamber. The NH3 reacts with the metal-organic precursor on the substrate to obtain a reaction product photoresist on the substrate surface.The second precursor also forms self-saturating bonds with the underlying reactive species to obtain another self-limiting and self-saturating second half-reaction. In some embodiments, a second rinsing operation is performed to remove unused reactants and reaction byproducts. The pulses of the first and second precursors are alternated with intervening rinsing operations until a desired photoresist layer thickness is achieved. 15 has been achieved.

[0053] In some embodiments, the photoresist layer 15The photoresist layer is formed to a thickness of approximately 5 nm to approximately 50 nm, and in other embodiments to a thickness of approximately 10 nm to approximately 30 nm. The person skilled in the art will recognize that further thickness ranges within the above-mentioned explicit ranges are conceivable and fall within the scope of this disclosure. The thickness can be evaluated using non-contact methods of X-ray reflection 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 coatings with high uniformity on larger substrates, the uniformity of the photoresist layer can be assessed with a 1-centimeter edge exclusion, meaning that the uniformity of the layer is not evaluated for sections of the coating within 1 centimeter of the edge. The person skilled in the art will recognize that further areas within the explicitly mentioned above are also considered and are within the scope of this disclosure.

[0054] 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.

[0055] A photoresist layer deposition device200 According to some embodiments of the disclosure, in Fig. Figure 8 shows the separation device. In some embodiments, the separation device is 200 an ALD or CVD device. The separation device 200 features a vacuum chamber 205 on. 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 has 210 a heater. In some embodiments, a first precursor or compound gas supply is used. 220 and a carrier / purge gas supply 225 via a gas pipeline 235 with an entrance 230 connected in the chamber, and a second precursor or compound gas supply 240 and a carrier / purge gas supply 225 are via another gas pipeline 235' with a different entrance 230'connected in the chamber. The chamber is emptied, and excess reactants and reaction byproducts are removed by a vacuum pump. 245 via an outlet 250 and a discharge line 255 removed. In some embodiments, the flow rate or pulses of precursor gases and carrier / purge gases, the removal of excess reactants and reaction byproducts, and the pressure inside the vacuum chamber are controlled. 205 and the temperature of the vacuum chamber 205 or the wafer support table 210 through a controller 260 controlled, which is configured to control each of these parameters.

[0056] In some embodiments, the organometallic compound contains tin (Sn), antimony (Sb), bismuth (Bi), indium (In), and / or tellurium (Te) as the metal component; however, the 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 metals may be used alternatively or in addition to Sn, Sb, Bi, In, and / or Te.

[0057] 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 exhibit strong absorption of extreme ultraviolet light at 13.5 nm. Hafnium offers good absorption of electron beam and extreme UV radiation. Metal compositions containing titanium, vanadium, molybdenum, or tungsten have strong absorption at longer wavelengths, for example, to provide sensitivity to ultraviolet light with a wavelength of 248 nm.

[0058] In some embodiments, the ALD or CVD deposition parameters are varied during the deposition operation to form a photoresist layer with a density gradient. In some embodiments, the photoresist layer possessing a density gradient reduces defects such as scum and bridging and improves linewidth roughness (LWR) and line edge roughness (LER).

[0059] Fig. Figure 9 shows a reaction that the components of the photoresist composition undergo as a result of the action of actinic radiation and heating according to an embodiment of the disclosure. Fig. Figure 9 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 9, the photoresist composition contains a metal-organic compound, for example SnX2R2, and a second compound, for example ammonia (NH3). When the metal-organic compound and the ammonia are combined, the metal-organic compound reacts with a portion of the ammonia in the vapor phase, forming a reaction product with amine groups bonded 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, thereby preventing contamination of the deposition chamber and semiconductor processing equipment by the metal in the metal-containing photoresist.Furthermore, the hydrogen bonds of the amine groups can counteract the effects of moisture on the quality of the photoresist layer.

[0060] When subsequently exposed to extreme ultraviolet radiation using a mask, the organometallic compound absorbs the extreme ultraviolet radiation, and one or more organic R groups are cleaved from the organometallic compound to form an amino-metal compound in the radiation-exposed areas. Then, when post-exposure bake (PEB) firing is performed, the amino-metal compounds crosslink in some embodiments via the amine groups, as shown in Fig. Figure 9 shows that in some embodiments, partial crosslinking of the amino-metal compounds occurs as a result of contact with extreme ultraviolet radiation. The selectively exposed photoresist is then developed, and the crosslinked, irradiated structure remains above the substrate, while the unirradiated areas are removed during development.

[0061] In some embodiments, a layer to be structured (target layer) 60 arranged before the formation of the photoresist layer above the substrate, as in Fig. 10 shown. In some embodiments, the layer to be structured is 60 a metallization layer or a dielectric layer, such as a passivation layer, arranged over a metallization layer. In embodiments in which the layer to be structured 60 a metallization layer, the layer to be structured 60formed from a conductive material using metallization processes and metal deposition techniques, including chemical vapor deposition, atomic layer deposition, and physical vapor deposition (sputtering). When the layer to be structured 60 A dielectric layer is the layer to be structured. 60 equally formed by techniques for creating dielectric layers, for example thermal oxidation, chemical vapor deposition, atomic layer deposition and physical vapor deposition.

[0062] The photoresist layer 50 is then selectively treated with actinic radiation 45 irradiated to expose regions 50 and unexposed regions 52 to form in the photoresist layer, as in the Fig. 11A and Fig. 11B shown and in the present text with regard to the Fig. 3A and Fig. 3B described. As explained in the present text, in some embodiments the photoresist is a negative-tone photoresist.

[0063] The unexposed photoresist regions 52 are through the submission of developers 57 from a dispensing device 62 , as in Fig. 12A shown, or by a dry development operation, as in Fig. 12B shown, developed to form a photoresist structure 55 to form, as in Fig. 13 shown. The development operation is similar to the one described here with reference to the Fig. 4A, Fig. 4B and Fig. 5 is explained.

[0064] Then, as in Fig. 14 shown, the structure 55 in the photoresist layer 15 using an etching operation to the layer to be structured 60 transferred, and the photoresist layer is removed, as described in reference to Fig. 6 explains, in order to structure the layer 60 a structure 55" to form.

[0065] In some embodiments, the photoresist layer 15 prior to the selective or structure-wise exposure of the photoresist layer with infrared, visible or near-ultraviolet radiation 110 irradiated to reduce or prevent outgassing of the photoresist layer, as in Fig. Figure 15 shows that exposure with infrared, visible, or near-ultraviolet radiation is performed with a lower exposure dose than the subsequent structure-wise exposure. In some embodiments, exposure with infrared, visible, or near-ultraviolet radiation increases the film density and reduces problems caused by moisture. In some embodiments, the photoresist layer is thermally treated prior to selective or structure-wise exposure to increase the photoresist layer's density. In some embodiments, the thermal treatment involves heating the photoresist layer to a temperature of approximately 40 °C and 120 °C for about 10 seconds to about 10 minutes. The photoresist layer and the substrate are then exposed as described in this text with respect to the Fig. 3A-6 and the Fig. 11A-14 described and processed.

[0066] In some embodiments, the photoresist layer contains 15 organometallic compounds or precursors that have one or more unsaturated bonds interacting with functional groups of an underlying substrate 10 can be coordinated, as in Fig. 16A shown. As in Fig. As shown in Figure 16B, the photoresist (PR) in its deposited state contains unsaturated bonds at an uncoordinated position. Upon heating the photoresist layer 15 Functional groups, such as hydroxyl groups, react on the surface of the substrate. 10 or an intermediate layer with the unsaturated bonds and bind the photoresist layer 15 chemically attached to the substrate 10 or the intermediate layer, which improves the adhesion of the photoresist to the substrate. Then the photoresist layer and the substrate are treated as described in the present text with respect to the Fig. 3A-6 and the Fig. 11A-14 describes how the substrate is processed. In some embodiments, the substrate is a silicon substrate, such as a silicon wafer, or a silicon layer.

[0067] In some embodiments, a capping layer is used. 130 applied to the photoresist layer before the photoresist layer 15 selectively or structurally exposed or cross-linked, as in Fig. 17 shown. The cap layer 130 In some embodiments, the capping layer is a non-metallic layer, such as silicon oxide or silicon nitride, or in other embodiments, a polymer layer. In some embodiments, the capping layer 130 deposited by atomic layer deposition, chemical vapor deposition, or spin coating. In some embodiments, the capping layer 130 deposited in the same chamber as the photoresist layer. In some embodiments, the capping layer helps130 to prevent outgassing of the photoresist or metal contamination. Furthermore, the capping layer can 130 to help prevent moisture from affecting the photoresist layer. In some embodiments, the capping layer has a thickness in the range of about 0.5 nm to about 10 nm. In other embodiments, the thickness of the capping layer ranges from about 1 nm to about 5 nm. In some embodiments, thicknesses below 0.5 nm are too thin to effectively prevent outgassing of the resist and the effects of moisture on the resist layer, and thicknesses above 10 nm offer no additional benefit over thicknesses of 10 nm. Then the photoresist layer and the substrate are connected as described in the present text with respect to the Fig. 3A-6 and the Fig. 11A-14 described and processed. The capping layer 130In some embodiments, the capping layer is removed either before, during, or after the development operation. In some embodiments, the capping layer is removed before structure-wise exposure.

[0068] In some embodiments, the substrate surface is treated with hexamethyldisilazane (HMDS) before the photoresist layer is formed over the substrate. In some embodiments, an amorphous carbonaceous sublayer is formed. 115 (or simply “sublayer”) formed above the substrate before the photoresist layer 15 is formed, as in Fig. 18 shown. In some embodiments, the sublayer reduces 115 the harmful effects of moisture, and in some embodiments the underlayer improves 115 the adhesion of the photoresist layer 15 on the substrate 10 In some embodiments, the amorphous carbon sublayer 115a carbon-based polymer layer. In some embodiments, the sublayer 115 an amorphous carbon-containing layer formed by chemical vapor deposition. In some embodiments, the sublayer 115 deposited by a variety of different techniques, for example by plasma-induced polymerization of unsaturated monomeric precursors such as ethylene, propylene, acetylene, or another volatile hydrocarbon-based precursor. In some embodiments, the sublayer 115 a thickness in the range of approximately 0.5 nm to approximately 10 nm. In other embodiments, the thickness of the sublayer ranges 115 from about 1 nm to about 5 nm. In some embodiments, the sublayer improves 115 the adhesion of the photoresist layer 15 on the surface of the substrate 10In some embodiments, thicknesses below 0.5 nm are too thin to effectively reduce the effects of moisture or the adhesion of the photoresist to the substrate. 10 to improve, and thicknesses above 10 nm offer no additional advantage over thicknesses of 10 nm. Then the photoresist layer and the substrate are as described in the present text with respect to the Fig. 3A-6 and the Fig. 11A-13 described and processed. The exposed sections of the sublayer 115 In some embodiments, they are removed by etching.

[0069] In some embodiments, an organic silane is applied to the photoresist layer before the photoresist layer is applied. 15 selectively or structurally exposed or cross-linked to form an organic silane layer 120 to form, as in Fig. Figures 19A-19C show that in some embodiments, the organic silane capping layer helps to prevent outgassing of the photoresist or metal contamination. Furthermore, the top layer can help prevent moisture from affecting the photoresist layer. Fig. 19B is a detailed view of Fig. 19A, showing the organic silane Y attached to the metal-organic precursor or metal-organic compound in the resist layer 15is bound. The organic silane Y can be any suitable organic silane. In some embodiments, the organic silane is one or more selected from the group consisting of trisilylamine, 1,3,5-trisilacyclohexane, 1,3,5-trisilapentane, bis(diethylamino)silane, bis(tertiary butylamino)silane, dichlorosilane, dibromosilane, diiodosilane, and disilane. In some embodiments, the organic silane is deposited by atomic layer deposition or chemical vapor deposition. An example of a reaction between an organic silane and the resist layer is shown in Fig. Figure 19C shows that the organic silane (organosilane) is deposited above the photoresist layer and coordinates with the organometals in the resist layer. In some embodiments, the organic silane is deposited in the same chamber on top of the photoresist layer. Then the photoresist layer and the substrate are arranged as described in this text with respect to the Fig. 3A-6 and the Fig. 11A-14 described in the process. In some embodiments, the organic silane layer is processed. 120 removed during or after the developmental surgery.

[0070] Other embodiments include other operations before, during, or after the operations described above. In some embodiments, the disclosed methods include the formation of fin field-effect transistor (FinFET) structures. In some embodiments, multiple active fins 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 sparing the STI features to form fin-like active regions. In some embodiments, one or more gate electrodes are formed on the substrate.In some embodiments, gate spacers, doped source / drain regions, contacts for gate / source / drain features, etc., are formed. In other embodiments, a target structure is formed as metal conductors in a multilayer interconnect structure. For example, the metal conductors can be formed in an interlayer dielectric (ILD) layer of the substrate, which has been etched to form multiple 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 examples are non-limiting examples of devices / structures that can be manufactured and / or improved using the methods described here.

[0071] In some embodiments, active components such as diodes, field-effect transistors (FETs), metal-oxide-semiconductor field-effect transistors (MOSFETs), complementary metal-oxide-semiconductor transistors (CMOS transistors), bipolar transistors, high-voltage transistors, high-frequency transistors, FinFETs, other three-dimensional FETs (3D-FETs), metal-oxide-semiconductor field-effect transistors (MOSFETs), complementary metal-oxide-semiconductor transistors (CMOS transistors), bipolar transistors, high-voltage transistors, high-frequency transistors, other memory cells, and combinations thereof are formed according to embodiments of the disclosure.

[0072] Methods for forming semiconductors and resist structuring according to the present disclosure allow for a higher utilization rate of resist material and a reduced use of potentially toxic organic solvents compared to solvent-based photoresists. Embodiments of the disclosure provide a uniform photoresist film that is deposited on the surface of a semiconductor substrate. Toxic organic solvents can be essentially eliminated from the photoresist structuring process because the photoresist is solvent-free, and in some embodiments, dry development is performed 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 the embodiments of the disclosure. These embodiments provide improved structural resolution. Furthermore, the one-pot deposition methods according to these embodiments achieve improved efficiency in the fabrication of semiconductor devices.

[0073] The dry structuring techniques disclosed in this text can offer several advantages over wet structuring. For example, the dry deposition techniques described here can be used to deposit thinner and defect-free films than can be applied using spin coating techniques, and the precise thickness of the deposited film can be modulated and controlled by increasing or decreasing the length of the deposition step or sequence. Accordingly, a dry process can offer a higher degree of tunability and allow for enhanced control of the critical dimension (CD) and improved skimming removal. Dry development can improve performance by preventing line collapse due to surface tension in wet development and increase throughput by avoiding a wet development track.Embodiments of the disclosure offer improved conductor width roughness and improved discrimination between exposed and unexposed regions of the photoresist.

[0074] One embodiment of the disclosure is a method for producing a semiconductor device, comprising forming a photoresist layer over a substrate, including combining a first precursor and a second precursor in a vapor state to form a photoresist material, wherein the first precursor is an organometal with the following formula: M a R b X c, where 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, and 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. The second precursor is at least one of an amine, a borane, and a phosphine. Photoresist formation involves depositing the photoresist material over the substrate. The photoresist layer is selectively irradiated with actinic radiation to form a latent structure, and the latent structure is developed by applying a developer to the selectively irradiated photoresist layer to form a structure. In one embodiment, the actinic radiation is extreme ultraviolet radiation.In one embodiment, the method comprises selectively exposing the photoresist layer to actinic radiation to form a latent structure and developing the latent structure by firing the photoresist layer. In one embodiment, the alkyl, alkenyl, or carboxylate group is substituted by one or more fluorine groups. In another embodiment, the sulfonate group is substituted by one or more amine groups. In one embodiment, the photoresist material is deposited onto the substrate by atomic layer deposition (ALD) or chemical vapor deposition (CVD). In another embodiment, the method comprises exposing the photoresist layer to infrared, visible, or near-ultraviolet radiation before selectively exposing the photoresist layer to actinic radiation.In one embodiment, the method comprises forming an amorphous carbon-containing layer over the substrate prior to forming the photoresist layer. In another embodiment, the method comprises forming a carbon-based polymer layer over the substrate prior to forming the photoresist layer. In another embodiment, the method comprises depositing an organic silane onto the photoresist layer prior to selectively irradiating the photoresist layer with actinic radiation. In one embodiment, the amine is ammonia or hydrazine. In another embodiment, the method comprises forming silicon oxide or silicon nitride over the photoresist layer prior to selectively irradiating the photoresist layer.

[0075] Another embodiment of the disclosure is a method for manufacturing a semiconductor device, comprising the deposition of a photoresist composition having a first compound and a second compound over a substrate surface by means of atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form a photoresist layer. The deposition of a photoresist layer comprises combining the first compound and the second compound in a vapor state to form the photoresist composition, wherein the first compound is at least one of the following: sec-hexyl-tris(dimethylamino), t-hexyl-tris(dimethylamino)-tin, i-hexyl-tris(dimethylamino)-tin, n-hexyl-tris(dimethylamino)-tin, sec-pentyl-tris(dimethylamino)-tin, t-pentyl-tris(dimethylamino)-tin, i-pentyl-tris(dimethylamino)-tin, n-pentyl-tris(dimethylamino)-tin, sec-butyl-tris(dimethylamino)-tin, t-butyl-tris(dimethylamino)-tin, i-butyl-tris(dimethylamino)-tinn-Butyl-tris(dimethylamino)-tin, sec-butyl-tris(dimethylamino)-tin, i-propyl-tris(dimethylamino)-tin, n-propyl-tris(diethylamino)-tin and analogous alkyl-tris(t-butoxy)-tin compounds, including sec-hexyl-tris(t-butoxy), t-Hexyl-tris(t-butoxy)-tin, i-hexyl-tris(t-butoxy)-tin, n-hexyl-tris(t-butoxy)-tin, sec-pentyl-tris(t-butoxy), t-pentyl-tris(t-butoxy)-tin, i-pentyl-tris(t-butoxy)-tin, n-Pentyltris(t-butoxy)-tin, t-Butyl-tris(t-butoxy)-tin, i-Butyl-tris(butoxy)-tin, n-Butyl-tris(butoxy)-tin, sec-Butyl-tris(butoxy)-tin, i-Propyl-(tris)dimethylamino-tin, or n-Propyl-tris(butoxy)-tin. The second compound is at least one of an amine, a borane, and a phosphine. The photoresist layer is selectively exposed to actinic radiation to form a latent structure. The latent structure is developed by applying a developer to the selectively exposed photoresist layer to form a structure.which exposes a section of the substrate surface. A section of the substrate exposed by development is removed. In one embodiment, removing a section of the substrate by development includes etching the substrate. In one embodiment, the actinic radiation is extreme ultraviolet radiation. In one embodiment, the method includes, after selectively exposing the photoresist layer with actinic radiation to form a latent structure and before developing the latent structure, heating the photoresist layer to a temperature in the range of 100 °C to 200 °C. In one embodiment, the first compound is substituted by one or more fluorine groups. In one embodiment, the developer is a dry developer. In one embodiment, the method includes exposing the photoresist layer with infrared, visible, or near-ultraviolet radiation.before the photoresist layer is selectively exposed to actinic radiation. In one embodiment, the method comprises forming an amorphous carbon layer over the substrate before forming the photoresist layer. In one embodiment, the amorphous carbon layer is a polymer layer. In one embodiment, the method comprises applying an organic silane to the photoresist layer before selectively exposing the photoresist layer to actinic radiation. In one embodiment, the amine is ammonia or hydrazine. In one embodiment, the method comprises forming a silicon oxide or silicon nitride over the photoresist layer before selectively exposing the photoresist layer.

[0076] Another embodiment of the disclosure is a method for fabricating a semiconductor device, comprising the simultaneous introduction of a first compound and a second compound into a chamber to form a composition of the first compound and the second compound. The composition of the first compound and the second compound is deposited onto a substrate by chemical vapor deposition (CVD) to form a layer of the composition. The first compound is an organometallic compound, and the second compound is selected from the group consisting of an amine, a borane, a phosphine, and combinations thereof. The layer of the composition is structure-patterned with actinic radiation to form a latent structure, and the structure-patterned layer of the composition is developed to form a structured layer of the composition.In one embodiment, the amine, borane, or phosphine contains a halide substituent. In one embodiment, the process comprises irradiating the layer of the composition with infrared, visible, or near-ultraviolet radiation prior to selectively irradiating the layer of the composition with actinic radiation. In one embodiment, the process comprises forming a polymer layer over the substrate before depositing the composition. In one embodiment, the process comprises applying an organic silane to the layer of the composition prior to selectively irradiating the layer of the composition with actinic radiation. In one embodiment, the actinic radiation is extreme ultraviolet radiation.In one embodiment, the method comprises heating the layer of the composition to a temperature in the range of 100 °C to 200 °C after structure-wise exposure of the layer of the composition with actinic radiation to form a latent structure and before developing the latent structure. In another embodiment, the method comprises removing an exposed section of the substrate after development. In another embodiment, removing a section of the substrate by development comprises etching the substrate. In another embodiment, development is a dry development operation. In another embodiment, the amine is ammonia or hydrazine. In another embodiment, the method comprises forming a silicon oxide or silicon nitride over the layer of the composition before selectively exposing the layer of the composition.

[0077] Another embodiment of the disclosure is a method for structuring a resist layer, comprising the deposition of 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 a non-silicon organometallic compound and a compound selected from the group consisting of an amine, a borane, and a phosphine. The resist layer is structure-crosslinked to form a latent structure within the resist layer. The latent structure is developed by applying a developer to the structure-crosslinked resist layer to form a structure that exposes a portion of the substrate surface. In one embodiment, the method includes removing a portion of the substrate exposed by development.In one embodiment, the organometallic compound contains a metal selected from the group consisting of Sn, Bi, Sb, In, and Te. In another embodiment, the organometallic compound contains a substituted or unsubstituted alkyl, alkenyl, or carboxylate group. In another embodiment, the organometallic compound contains a halide or sulfonate group. In another embodiment, the sulfonate group is substituted by one or more amine groups. In another embodiment, the amine, borane, or phosphine contains a halide substituent. In another embodiment, the structure-wise crosslinking of the resist layer comprises structure-wise exposure of the resist layer to extreme ultraviolet radiation and heating of the structure-wise exposed resist layer. In another embodiment, the structure-wise exposed resist layer is heated to a temperature in the range of 100 °C to 200 °C.In one embodiment, the method comprises irradiating the resist layer with infrared, visible, or near-ultraviolet radiation before the resist layer is selectively crosslinked. In one embodiment, the amine is ammonia or hydrazine. In another embodiment, the method comprises forming a silicon oxide or silicon nitride over the resist layer prior to selectively crosslinking the resist layer.

[0078] Another embodiment of the disclosure is a method for forming a structured layer over a substrate surface, comprising the deposition of a reaction product of a metal-organic compound in the vapor phase and a second compound in the vapor phase over a substrate to form a resist layer. The metal-organic compound has the formula: M a R b X c, where 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, and 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 compound in the vapor phase is selected from the group consisting of an amine, a borane, a phosphine, and combinations thereof. The resist layer is structure-wise crosslinked to form a latent structure within the resist layer. The latent structure is developed by applying a developer to the structure-wise crosslinked resist layer to form a structure that exposes a section of the substrate surface. In one embodiment, X is a sulfonate group substituted by one or more amine groups. In another embodiment, the amine, borane, or phosphine contains a halide substituent.In one embodiment, the structure-wise crosslinking of the resist layer comprises structure-wise exposure of the resist layer with extreme ultraviolet radiation and heating of the structure-wise exposed resist layer. In one embodiment, the structure-wise crosslinked resist layer is heated to a temperature in the range of 100 °C to 200 °C. In one embodiment, the method comprises removing a section of the substrate exposed by development. In one embodiment, the method comprises heating the resist layer to a temperature in the range of 40 °C to 120 °C prior to structure-wise crosslinking of the resist layer. In one embodiment, the method comprises forming an amorphous carbon layer over the substrate prior to forming the resist layer. In one embodiment, the amorphous carbon layer is a polymer layer.In one embodiment, the method comprises applying an organic silane to the resist layer prior to the structural crosslinking of the resist layer. In one embodiment, the amine is ammonia or hydrazine. In another embodiment, the method comprises forming a silicon oxide or silicon nitride over the resist layer prior to the structural crosslinking of the resist layer.

[0079] Another embodiment of the disclosure is a method for structuring a photoresist layer, comprising the deposition of a photoresist layer over a substrate by a vapor deposition operation. The photoresist layer comprises a reaction product of a silicon-free organometallic compound and a compound selected from the group consisting of an amine, a borane, a phosphine, and combinations thereof. The photoresist layer is selectively irradiated with actinic radiation to form a latent structure within the photoresist layer. Sections of the photoresist layer that were not irradiated with actinic radiation are removed to form a structure from the remaining sections of the photoresist layer that were irradiated during the selective irradiation of the photoresist layer with actinic radiation.In one embodiment, the method comprises removing sections of the substrate exposed by the removed sections of the photoresist layer. In another embodiment, removing sections of the substrate comprises dry etching of the substrate. In another embodiment, removing sections of the photoresist layer comprises applying a plasma to the photoresist layer. In another embodiment, the vapor deposition operation comprises atomic layer deposition or chemical vapor deposition. In another embodiment, the amine, borane, or phosphine contains a halide substituent. In another embodiment, the actinic radiation is extreme ultraviolet radiation. In another embodiment, after selectively irradiating the photoresist layer with actinic radiation, the method comprises heating the photoresist layer to a temperature in the range of 100 °C to 200 °C.In one embodiment, the method comprises exposing the photoresist layer to infrared, visible, or near-ultraviolet radiation prior to selectively exposing the photoresist layer to actinic radiation. In another embodiment, the method comprises heating the photoresist layer to a temperature of 40 °C to 120 °C prior to selectively exposing the photoresist layer to actinic radiation. In one embodiment, the amine is ammonia or hydrazine. In another embodiment, the method comprises forming a silicon oxide or silicon nitride over the photoresist layer prior to selectively exposing the photoresist layer.

[0080] The above outlines features of various embodiments or examples so that the person skilled in the art can better understand the aspects of the present disclosure. It is clear to the person skilled in the art 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 in the embodiments or examples presented in this text. It should also be clear to the person skilled in the art that such equivalent designs do not depart from the essence and scope of protection of the present disclosure, and that they can make various changes, substitutions, and modifications to the present invention without departing from the essence and scope of protection 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 63002247

[0001] US 63025957

[0001]

Claims

[1] Method for manufacturing a semiconductor device comprising: Forming a photoresist layer over a substrate, including: - Combining a first precursor and a second precursor in a vapor state to form a photoresist material, where the first precursor is an organometal with the following formula: M a R b X c where 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 and Lu, where R is a substituted or unsubstituted alkyl, alkenyl or carboxylate group, where X is a halide or sulfonate group, and where 1 ≤ a ≤ 2, b ≥ 1, c ≥ 1, and b + c ≤ 5, and wherein the second precursor is at least one of an amine, a borane and a phosphine; and - Deposition of the photoresist material onto the substrate; Selective exposure of the photoresist layer with actinic radiation to form a latent structure; and Developing the latent structure by applying a developer to the selectively exposed photoresist layer to form a structure. [2] Method according to claim 1, wherein the actinic radiation is extreme ultraviolet radiation. [3] Method according to claim 1 or 2, further comprising: Burning of the photoresist layer after selective exposure of the photoresist layer with actinic radiation to form a latent structure, and before developing the latent structure. [4] Method according to any of the preceding claims, wherein the alkyl, alkenyl or carboxylate group is substituted by one or more fluoro groups. [5] Method according to any of the preceding claims, wherein the sulfonate group is substituted by one or more amine groups. [6] Method according to any of the preceding claims, wherein the photoresist material is deposited over the substrate by ALD or CVD. [7] Method according to any of the preceding claims, further comprising: Exposure of the photoresist layer with infrared, visible or near-ultraviolet radiation, prior to selective exposure of the photoresist layer with actinic radiation. [8] Method according to any of the preceding claims, further comprising: Formation of an amorphous, carbon-containing layer over the substrate prior to the formation of the photoresist layer. [9] Method according to any of the preceding claims, further comprising: Formation of a carbon-based polymer layer over the substrate prior to the formation of the photoresist layer. [10] Method according to any of the preceding claims, further comprising: Application of an organic silane to the photoresist layer prior to selective exposure of the photoresist layer with actinic radiation. [11] Method for manufacturing a semiconductor device comprising: Deposition of a photoresist composition containing a first compound and a second compound over a substrate surface by ALD or CVD to form a photoresist layer, including the deposition of a photoresist composition: - Combining the first compound and the second compound in a vapor state to form the photoresist composition, wherein the first compound is at least one of the following: sec-hexyltris(dimethylamino), t-hexyltris(dimethylamino)-tin, i-hexyltris(dimethylamino)-tin, n-hexyltris(dimethylamino)-tin, sec-pentyltris(dimethylamino)-tin, t-pentyltris(dimethylamino)-tin, i-pentyltris(dimethylamino)-tin, n-pentyltris(dimethylamino)-tin, sec-butyltris(dimethylamino)-tin, t-butyltris(dimethylamino)-tin, i-butyltris(dimethylamino)-tin n-Butyl-tris(dimethylamino)-tin, sec-butyltris(dimethylamino)-tin, i-propyl-tris(dimethylamino)-tin, n-propyltris(diethylamino)-tin and analogous alkyl-tris(t-butoxy)-tin compounds, including sec-hexyl-tris(t-butoxy), t-Hexyl-tris(t-butoxy)-tin, i-hexyltris(t-butoxy)-tin, n-hexyl-tris(t-butoxy)-tin, sec-pentyl-tris(t-butoxy), t-pentyl-tris(t-butoxy)-tin, i-pentyl-tris(t-butoxy)-tin, n-Pentyl-tris(t-butoxy)-tin,t-Butyl-tris(t-butoxy)-tin, i-Butyl-tris(butoxy)-tin, n-Butyltris(butoxy)-tin, sec-Butyl-tris(butoxy)-tin, i-Propyl-(tris)dimethylamino-tin or n-Propyl-tris(butoxy)-tin, and the second compound is at least one of an amine, a borane and a phosphine; and , - selective exposure of the photoresist layer with actinic radiation to form a latent structure; Developing the latent structure by applying a developer to the selectively exposed photoresist layer to form a structure that exposes a section of the substrate surface; and Removing a section of the substrate that was exposed during development. [12] Method according to claim 11, wherein the removal of a section of the substrate by developing etching of the substrate comprises. [13] Method according to claim 11 or 12, wherein the actinic radiation is extreme ultraviolet radiation. [14] Method according to any one of the preceding claims 11 to 13, further comprising: Heating the photoresist layer to a temperature of 100 °C to 200 °C after selective exposure of the photoresist layer with actinic radiation to form a latent structure, and before developing the latent structure. [15] Method according to any one of the preceding claims 11 to 14, wherein the first compound is substituted by one or more fluorogroups. [16] Method for manufacturing a semiconductor device, comprising: Simultaneous introduction of a first compound and a second compound into a chamber to form a composition of the first compound and the second compound; Deposition of the composition of the first compound and the second compound over a substrate by CVD to form a layer of the composition, wherein the first compound is an organometallic compound and the second compound is selected from the following: an amine, a borane, a phosphine and combinations thereof; Structure-wise exposure of the layer from the composition with actinic radiation to form a latent structure; and Developing the structurally exposed layer from the composition to form a structured layer of the composition. [17] Method according to claim 16, wherein the amine, borane or phosphine contains a halide substituent. [18] Method according to claim 16 or 17, further comprising: Exposure of the layer from the composition with infrared, visible or near-ultraviolet radiation prior to structure-wise exposure of the layer from the composition with actinic radiation. [19] Method according to any one of the preceding claims 16 to 18, further comprising: Forming a polymer layer over the substrate prior to depositing the composition. [20] Method according to any one of the preceding claims 16 to 19, further comprising: Application of an organic silane to the layer of the composition prior to selectively irradiating the layer of the composition with actinic radiation.