Method for manufacturing semiconductor device

Abstract

The present application relates to a method for manufacturing a semiconductor device, including forming a photoresist layer over a substrate. Forming the photoresist layer includes combining a first precursor and a second precursor in a vapor state to form a photoresist material, wherein the first precursor is a material having a formula M a R b X c An organic metal, wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce or Lu; R is a substituted or unsubstituted alkyl, alkenyl or carboxylate group; X is a halogen 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 or a phosphine. Forming a photoresist layer includes depositing a photoresist on a substrate. The photoresist layer is selectively exposed to actinic radiation to form a latent pattern, and the latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern.

Description

Technical Field

[0001] The present disclosure relates to a method for manufacturing a semiconductor device. Background Art

[0002] As consumer devices become smaller in response to consumer demand, the individual components of these devices must also decrease in size. Semiconductor devices that constitute the main components of devices such as mobile phones, computer tablets, etc. have been forced to become smaller and smaller, which in turn has forced the individual devices within the semiconductor devices (e.g., transistors, resistors, capacitors, etc.) to decrease in size.

[0003] One enabling technology used in the manufacture of semiconductor devices is the use of photolithographic materials. Such materials are applied to the surface of the layer to be patterned and then exposed to energy that has itself been patterned. Such exposure changes the chemical and physical properties of the exposed areas of the photosensitive material. This modification, and the lack of modification in the unexposed areas of the photosensitive material, can be exploited to remove one area without removing another area.

[0004] However, as the size of individual devices decreases, the process window for lithographic processing becomes increasingly tighter. Thus, advances in the field of lithographic processing are necessary to maintain the ability to scale down devices, and further improvements are needed to meet the desired design standards so that the march toward smaller and smaller components can be maintained. Summary of the invention

[0005] According to one embodiment of the present disclosure, there is provided a method for manufacturing a semiconductor device, comprising:

[0006] A photoresist layer is formed over the substrate, comprising:

[0007] combining a first precursor and a second precursor in a vapor state to form a photoresist material,

[0008] Wherein the first precursor is a compound having the formula M a R b X c Organometallics:

[0009] wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce or Lu,

[0010] R is a substituted or unsubstituted alkyl, alkenyl or carboxylate group,

[0011] X is a halogen or a sulfonate group, and

[0012] 1≤a≤2, b≥1, c≥1, and b+c≤5, and

[0013] The second precursor is at least one of an amine, a borane, or a phosphine; and

[0014] depositing the photoresist over a substrate;

[0015] selectively exposing the photoresist layer to actinic radiation to form a latent pattern; and

[0016] The latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern.

[0017] According to another embodiment of the present disclosure, there is provided a method for manufacturing a semiconductor device, comprising:

[0018] depositing a photoresist composition on a substrate surface by atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form a photoresist layer, wherein the photoresist composition includes a first compound and a second compound,

[0019] The deposited photoresist composition comprises:

[0020] combining the first compound and the second compound in a vapor state to form a photoresist composition,

[0021] The first compound is at least one of the following: secondary hexyl tris(dimethylamino)tin, tert-hexyl tris(dimethylamino)tin, isohexyl tris(dimethylamino)tin, n-hexyl tris(dimethylamino)tin, secondary amyl tris(dimethylamino)tin, tert-amyl tris(dimethylamino)tin, isopentyl tris(dimethylamino)tin, n-amyl tris(dimethylamino)tin, secondary butyl tris(dimethylamino)tin, tert-butyl tris(dimethylamino)tin, isobutyl tris(dimethylamino)tin, n-butyl tris(dimethylamino)tin, isopropyl tris(dimethylamino)tin, n-propyl tris(dimethylamino)tin tri(tert-butoxy)tin, tert-hexyltri(tert-butoxy)tin, isohexyltri(tert-butoxy)tin, n-hexyltri(tert-butoxy)tin, sec-amyltri(tert-butoxy)tin, tert-amyltri(tert-butoxy)tin, isopentyltri(tert-butoxy)tin, n-amyltri(tert-butoxy)tin, tert-butyltri(tert-butoxy)tin, isobutyltri(butoxy)tin, n-butyltri(butoxy)tin, sec-butyltri(butoxy)tin, isopropyltri(dimethylamino)tin, or n-propyltri(butoxy)tin, and

[0022] The second compound is at least one of an amine, a borane, or a phosphine, and

[0023] selectively exposing the photoresist layer to actinic radiation to form a latent pattern;

[0024] developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern exposing a portion of the substrate surface; and

[0025] The portions of the substrate exposed by the development are removed.

[0026] According to another embodiment of the present disclosure, there is provided a method for manufacturing a semiconductor device, comprising:

[0027] simultaneously introducing a first compound and a second compound into the chamber to form a composition of the first compound and the second compound;

[0028] depositing the composition of the first compound and the second compound on a substrate by chemical vapor deposition (CVD) to form a layer of the composition,

[0029] The first compound is an organic metal compound, and the second compound is selected from amines, boranes, phosphines and combinations thereof.

[0030] patternwise exposing the layer of the composition to actinic radiation to form a latent pattern; and

[0031] The pattern-wise exposed layer of the composition is developed to form a patterned layer of the composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] The present disclosure will be best understood from the following detailed description when read in conjunction with the accompanying drawings. It is emphasized that, in accordance with standard practice in the industry, various features are not drawn to scale and are used for illustration purposes only. In fact, the size of the various features may be arbitrarily increased or reduced for clarity of discussion.

[0033] Figure 1 A process flow for manufacturing a semiconductor device according to an embodiment of the present disclosure is shown.

[0034] Figure 2 The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0035] Figure 3A and Figure 3B The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0036] Figure 4A and Figure 4B The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0037] Figure 5 The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0038] Figure 6The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0039] Figure 7 An organometallic precursor according to an embodiment of the present disclosure is shown.

[0040] Figure 8 A photoresist deposition apparatus according to some embodiments of the present disclosure is shown.

[0041] Fig. 9 The reaction that a photoresist layer undergoes due to exposure to actinic radiation and heat according to one embodiment of the present disclosure is shown.

[0042] Fig.10 Process stages according to one embodiment of the present disclosure are shown.

[0043] Fig.11A and 11B Process stages according to one embodiment of the present disclosure are shown.

[0044] Fig. 12A and 12B The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0045] Fig.13 A sequential operation according to one embodiment of the present disclosure is shown.

[0046] Fig.14 The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0047] Fig.15 The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0048] Fig.16A shows the process stages of sequential operation according to one embodiment of the present disclosure, and Fig. 16B The reactions that a photoresist layer undergoes during the process stages are shown.

[0049] Fig.17 The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0050] Fig.18 The process stages are shown in sequential operation according to one embodiment of the present disclosure.

[0051] Fig.19A The process stages are shown in sequential operation according to one embodiment of the present disclosure. Fig.19B Shows Fig.19A Detailed diagram of. Fig.19C The reactions that the organometallic precursor undergoes are shown. DETAILED DESCRIPTION

[0052] It should be understood that the following disclosure provides many different embodiments or examples for realizing the different features of the present disclosure. Specific embodiments or examples of components and arrangements are described below to simplify the present disclosure. Of course, these are only examples and are not intended to be limiting. For example, the size of the element is not limited to the disclosed range or value, but may depend on the process conditions and / or the desired characteristics of the device. In addition, in the following description, forming a first feature above or on a second feature may include an embodiment in which the first feature and the second feature are formed to be in direct contact, and may also include an additional feature inserted between the first feature and the second feature, so that the first feature and the second feature may not be in direct contact. For simplicity and clarity, various features may be arbitrarily drawn in different proportions.

[0053] In addition, for ease of description, spatially relative terms such as "below", "below", "lower", "above", "upper", etc. may be used herein to describe the relationship of one element or feature as shown in the figure to another one or more elements or features. In addition to the orientation depicted in the figure, spatially relative terms are also intended to cover different orientations of the device in use or operation. The device can be oriented in other ways (rotated 90 degrees or in other orientations), and the spatially relative descriptors used in this article can be interpreted accordingly. In addition, the term "made of" can mean "including" or "consisting of".

[0054] As the semiconductor industry has progressed to nanotechnology process nodes in pursuit of higher device density, higher performance and lower cost, there are challenges in reducing semiconductor feature size. Extreme ultraviolet lithography (EUVL) has been developed to form smaller semiconductor device feature sizes and increase device density on semiconductor wafers. In order to improve EUVL, it is necessary to increase wafer exposure throughput. Wafer exposure throughput can be improved by increasing exposure power or increasing resist photospeed (sensitivity).

[0055] Metal-containing photoresists are used in extreme ultraviolet (EUV) lithography because metals have high absorption of EUV radiation, which increases the photoresist's photospeed. However, metal-containing photoresist layers can outgas during processing, which can cause the quality of the photoresist layer to vary over time and can cause contamination, which can negatively impact lithography performance and increase defects.

[0056] In addition, uneven exposure of the photoresist, especially at deeper portions of the photoresist layer, can result in uneven crosslinking of the photoresist. Less light energy reaches the lower portion of the photoresist layer, resulting in uneven exposure. Uneven exposure can result in poor line width roughness (LWR), which prevents the formation of a straight-edge resist profile.

[0057] Furthermore, because the solvents used in solvent-based photoresist formation and development can be toxic, a greener process for photoresist layer formation and subsequent patterning that does not use toxic solvents is needed.

[0058] Furthermore, the spin coating process may only use 2% to 5% of the material dispensed onto the substrate, while the remaining 95% to 98% is thrown off during the spin coating operation.A photoresist deposition operation with high material usage efficiency is desirable.

[0059] In addition, the density of the spin-coated photoresist film may not be uniform, and aggregation of the photoresist film may occur in some parts.

[0060] Additionally, the photoresist layer formation and patterning operations substantially reduce or prevent metal contamination of the processing chamber and metals.

[0061] In an embodiment of the present disclosure, the above problems are solved by depositing a photoresist on a substrate via a vapor deposition operation, wherein the vapor deposition operation includes atomic layer deposition (ALD) or chemical vapor deposition (CVD) of a photoresist material. The photoresist layer deposited by the vapor deposition operation according to an embodiment of the present disclosure provides a photoresist layer having a controllable film thickness and high film uniformity and density over a large deposition area. In addition, an embodiment of the present disclosure includes solvent-free photoresist layer formation, thereby providing a greener process. In addition, the photoresist deposition operation is a single pot method (performed in a single chamber), thereby improving manufacturing efficiency and limiting or preventing metal contamination of the processing chamber.

[0062] Figure 1 1 shows a process flow 100 for manufacturing a semiconductor device according to an embodiment of the present disclosure. In some embodiments, in operation S110, a resist is coated on the surface of the layer to be patterned or the substrate 10 to form a resist layer 15, such as Figure 2 As shown. In some embodiments, the resist is a metal-containing photoresist formed by CVD or ALD. Then, in some embodiments, the resist layer 15 undergoes a first heating operation 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 ten minutes.

[0063] After the optional first heating operation S120 or the resist deposition operation S110, the photoresist layer 15 is selectively exposed to actinic radiation 45 / 97 (see Figure 3A and Figure 3B ). In some embodiments, the photoresist layer 15 is selectively or pattern-wise exposed to ultraviolet radiation. In some embodiments, the ultraviolet radiation is deep ultraviolet radiation (DUV). In some embodiments, the ultraviolet radiation is extreme ultraviolet (EUV) radiation. In some embodiments, the photoresist layer is selectively or pattern-wise exposed to an electron beam.

[0064] like Figure 3A As shown, in some embodiments, exposure radiation 45 passes through photomask 30 before irradiating photoresist layer 15. In some embodiments, the photomask has a pattern to be replicated in photoresist layer 15. In some embodiments, the pattern is formed by an opaque pattern 35 on photomask substrate 40. Opaque pattern 35 can be formed of a material that is opaque to ultraviolet radiation (e.g., chromium), while photomask substrate 40 is formed of a material that is transparent to ultraviolet radiation (e.g., fused silica).

[0065] In some embodiments, EUV lithography is used to perform selective exposure or pattern-by-pattern exposure of the photoresist layer 15 to form exposed regions 50 and unexposed regions 52. In some embodiments, during the EUV lithography operation, a reflective photomask 65 is used to form a patterned exposure light, such as Figure 3B As shown. The reflective photomask 65 includes a low thermal expansion glass substrate 70 on which a reflective multilayer 75 of Si and Mo is formed. A capping 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. EUV radiation 95 is directed toward the reflective photomask 65 at an incident angle of about 6°. A portion 97 of the EUV radiation is reflected by the Si / Mo multilayer 75 toward the photoresist-coated substrate 10, while a portion of the EUV radiation incident on the absorber layer 85 is absorbed by the photomask. In some embodiments, additional optical devices including mirrors are provided between the reflective photomask 65 and the photoresist-coated substrate.

[0066] In some embodiments, exposure to radiation is performed by placing the photoresist-coated substrate in a lithography tool. The lithography tool includes a photomask 30 / 65, an optical device, an exposure radiation source that provides radiation 45 / 97 for exposure, and a movable stage for supporting and moving the substrate under the exposure radiation.

[0067] In some embodiments, optics (not shown) are used in the lithography tool to expand, reflect, or otherwise control the radiation 45 / 97 before or after it is patterned by the photomask 30 / 65. In some embodiments, the optics include one or more lenses, mirrors, filters, and combinations thereof to control the radiation 45 / 97 along the path of the optics.

[0068] In some embodiments, the radiation is electromagnetic radiation, such as g-line (wavelength of about 436 nm), i-line (wavelength of about 365 nm), ultraviolet radiation, far ultraviolet radiation, extreme ultraviolet, electron beam, etc. In some embodiments, the radiation source is selected from the group consisting of: mercury vapor lamp, xenon lamp, carbon arc lamp, KrF excimer laser (wavelength of 248 nm), ArF excimer laser (wavelength of 193 nm), F2 excimer laser (wavelength of 157 nm), or CO2 laser excited Sn plasma (extreme ultraviolet, wavelength of 13.5 nm).

[0069] The amount of electromagnetic radiation can be characterized by a flux or dose, which is obtained by integrating the radiation flux over the entire exposure time. In some embodiments, a suitable radiation flux is about 1 mJ / cm 2 About 150mJ / cm 2 , in other embodiments, about 2 mJ / cm 2 About 100mJ / cm 2 , in other embodiments, about 3 mJ / cm 2 to about 50mJ / cm 2 One of ordinary skill in the art will recognize that other ranges of radiant flux within the explicit ranges above are contemplated and within the present disclosure.

[0070] In some embodiments, selective or pattern-by-pattern exposure is performed by scanning an electron beam. With electron beam lithography, the electron beam induces secondary electrons, thereby changing the irradiated material. High resolution can be achieved using electron beam lithography and the metal-containing resists disclosed herein. The electron beam can be characterized by the energy of the beam, and in some embodiments, suitable energies are in the range of about 5V to about 200kV (kilovolts), and in other embodiments, in the range of about 7.5V to about 100kV. In some embodiments, the near-field corrected beam dose at 30kV is about 0.1μC / cm 2 to about 5μC / cm 2 In other embodiments, about 0.5 μC / cm 2 to about 1μC / cm 2 and in other embodiments, about 1 μC / cm 2 to about 100μC / cm2 One of ordinary skill in the art can calculate corresponding doses at other beam energies based on the teachings herein, and will recognize that other ranges of electron beam performance within the explicit ranges above are contemplated and within the present disclosure.

[0071] The regions of the photoresist layer exposed to the radiation 50 undergo a chemical reaction, thereby changing its susceptibility to removal in a subsequent development operation S150. In some embodiments, the portion of the photoresist layer exposed to the radiation 50 undergoes a reaction, making the exposed portion easier to remove during the development operation S150. In other embodiments, the portion of the photoresist layer exposed to the radiation 50 undergoes a reaction, making the exposed portion difficult to remove during the development operation S150.

[0072] Next, the photoresist layer 15 is subjected to a second heating or post-exposure bake (PEB) in operation S140. In some embodiments, the photoresist layer 15 is heated to a temperature of about 50° C. to about 250° C. for about 20 seconds to about 120 seconds. In some embodiments, the post-exposure bake is performed at a temperature ranging from about 100° C. to about 230° C., and in other embodiments at a temperature ranging from about 150° C. to about 200° C. In some embodiments, the post-exposure bake operation S140 causes the reaction product of the first compound or the first precursor to crosslink with the second compound or the second precursor.

[0073] The selectively exposed photoresist layer is then developed in operation S150. In some embodiments, the selectively exposed photoresist layer 15 is developed by applying a solvent-based developer 57 to the selectively exposed photoresist layer 15. Figure 4A As shown, liquid developer 57 is supplied from dispenser 62 to photoresist layer 15. In some embodiments, due to exposure to actinic radiation or post-exposure baking, exposed portions 50 of the photoresist undergo a cross-linking reaction, and unexposed portions of photoresist layer 52 are removed by developer 57, thereby forming a pattern of openings 55 in photoresist layer 15 to expose substrate 20, as shown in FIG. Figure 5 shown.

[0074] In some embodiments, the photoresist developer 57 comprises a solvent and an acid or a base. In some embodiments, the concentration of the solvent is about 60 wt % to about 99 wt % based on the total weight of the photoresist developer. The concentration of the acid or base is about 0.001 wt % to about 20 wt % based on the total weight of the photoresist developer. In certain embodiments, the concentration of the acid or base in the developer is about 0.01 wt % to about 15 wt % based on the total weight of the photoresist developer.

[0075] In some embodiments, the developer 57 is applied to the photoresist layer 15 using a spin coating process. In the spin coating process, the developer 57 is applied to the photoresist layer 15 from above the photoresist layer 15 while the substrate coated with the photoresist is rotated, such as Figure 4A As shown. In some embodiments, the developer 57 is supplied at a rate between about 5 ml / min and about 800 ml / min while the photoresist-coated substrate 10 is rotated at a speed between about 100 rpm and about 2000 rpm. In some embodiments, the developer is at a temperature between about 10° C. and about 80° C. In some embodiments, the development operation lasts from about 30 seconds to about 10 minutes.

[0076] In some embodiments, the developer 57 is an organic solvent. The organic solvent can be any suitable solvent. In some embodiments, the solvent is selected from one or more of the following: propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, 4-methyl-2-pentanol, acetone, methyl ethyl ketone, dimethylformamide (DMF), isopropyl alcohol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (MIBC), n-butyl acetate (nBA), 2-heptanone (MAK), tetrahydrofuran (THF), and dioxane.

[0077] Although a spin coating operation is a suitable method for developing the photoresist layer 15 after exposure, it is intended to be illustrative and not intended to limit the embodiments. Instead, any suitable developing operation may be used alternatively, including an immersion process, a puddle process, and a spray coating method. All such developing operations are included within the scope of the embodiments.

[0078] In some embodiments, Figure 4B As shown, dry developer 105 is applied to the selectively exposed photoresist layer 15. In some embodiments, dry developer 105 is plasma or chemical vapor, and dry development operation S150 is plasma etching or chemical etching operation. Dry development uses the difference related to composition, crosslinking degree and film density to selectively remove the resist of desired part. In some embodiments, dry development process uses gentle plasma (high pressure, low power) or thermal process in the vacuum chamber of heating, while making dry development chemicals such as BCl3, BF3 or other Lewis acids flow in vapor state. In some embodiments, BCl3 removes unexposed material, leaving the pattern of exposed film, which is transferred to the layer below by the etching process based on plasma.

[0079] In some embodiments, dry development includes a plasma process, including transformer coupled plasma (TCP), inductively coupled plasma (ICP), or capacitively coupled plasma (CCP). In some embodiments, the plasma process is performed at a pressure of about 5 mTorr to about 20 mTorr, a power level of about 250 W to about 1000 W, a temperature 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.

[0080] After the development operation, additional processing is performed while the patterned photoresist layer 50 is in place. For example, in some embodiments, an etching operation using dry etching or wet etching is performed to transfer the pattern of the photoresist layer 50 to the underlying substrate 10, thereby forming the recess 55', such as Figure 6 As shown. The substrate 10 has a different etching resistance than the photoresist layer 15. In some embodiments, the etchant is more selective to the substrate 10 than the photoresist layer 15.

[0081] In some embodiments, the exposed photoresist layer 15 is at least partially removed during the etching operation. In other embodiments, after etching the substrate 10 by selective etching, the exposed photoresist layer 15 is removed by using a suitable photoresist stripping solvent or by a photoresist plasma ashing operation.

[0082] In some embodiments, substrate 10 includes a single crystal semiconductor layer on at least a portion of its surface. Substrate 10 may include a single crystal semiconductor material, such as but not limited to Si, Ge, SiGe, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs, GaSbP, GaAsSb, and InP. In some embodiments, substrate 10 is a silicon layer of a SOI (silicon on insulator) substrate. In certain embodiments, substrate 10 is made of crystalline Si.

[0083] The substrate 10 may include one or more buffer layers (not shown) in its surface region. The buffer layer may be used to gradually change the lattice constant from the lattice constant of the substrate to the lattice constant of the subsequently formed source / drain region. The buffer layer may be formed of an epitaxially grown single crystalline semiconductor material, such as but not limited to Si, Ge, GeSn, SiGe, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs, GaSbP, GaAsSb, GaN, GaP, and InP. In one embodiment, a silicon germanium (SiGe) buffer layer is epitaxially grown on the silicon substrate 10. The germanium concentration of the SiGe buffer layer may increase from 30 atomic % of the bottommost buffer layer to 70 atomic % of the topmost buffer layer.

[0084] In some embodiments, the substrate 10 includes one or more layers of at least one metal, metal alloy, and metal having the formula MX a wherein M is a metal and X is N, S, Se, O, Si, and a is from about 0.4 to about 2.5. In some embodiments, substrate 10 comprises titanium, aluminum, cobalt, ruthenium, titanium nitride, tungsten nitride, tantalum nitride, and combinations thereof.

[0085] In some embodiments, substrate 10 includes a dielectric material having at least the formula MX b wherein M is a metal or Si, X is N or O, and b ranges from about 0.4 to about 2.5. In some embodiments, the substrate 10 comprises silicon dioxide, silicon nitride, aluminum oxide, hafnium oxide, lanthanum oxide, and combinations thereof.

[0086] The photoresist layer 15 is a photosensitive layer that is patterned by exposure to actinic radiation. Typically, the chemical properties of the photoresist areas struck by the incident radiation are changed in a manner that depends on the type of photoresist used. The photoresist layer 15 is a positive resist or a negative resist. A positive resist refers to a photoresist material that, when developed, portions of the photoresist layer exposed to actinic radiation (e.g., ultraviolet light) are removed, while areas of the photoresist that are not exposed (or less exposed) remain on the substrate after the development operation. On the other hand, a negative resist refers to a photoresist material that, when developed, portions of the photoresist layer exposed to actinic radiation (e.g., ultraviolet light) remain on the substrate after the development operation, while areas of the photoresist that are not exposed (or less exposed) are removed after the development operation.

[0087] In some embodiments, the photoresist layer 15 is made of a photoresist composition including a first compound or a first precursor and a second compound or a second precursor combined in a vapor state. The first precursor or the first compound is a photoresist having a formula M a R b X c Organic metals, such as Figure 7As shown, wherein M is selected from 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 Sn, Bi, In and Te. In some embodiments, R is a C3-C6 alkyl, alkenyl or carboxylate. In some embodiments, R is selected from propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, isohexyl, sec-hexyl, tert-hexyl and combinations thereof. In some embodiments, X is a ligand, ion or other fragment that reacts with a second compound or a second precursor; 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, such as Figure 7 As shown, each monomer unit is connected by an amine group. Each monomer has a formula M as defined above. a R b X c .

[0088] In some embodiments, R is an alkyl group, such as C n H 2n+1 , wherein n≥3. In some embodiments, R is fluorinated, for example having the formula C n F x H ((2n+1) -x). In some embodiments, R has at least one β-hydrogen or β-fluorine. In some embodiments, R is selected from a combination of isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, and sec-pentyl.

[0089] In some embodiments, X is any fragment that is easily replaced by a second compound or a second precursor to produce an M-OH fragment, such as a fragment selected from the group consisting of: amine (including dialkylamino and monoalkylamino); alkoxy; carboxylate, halogen and sulfonate. 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 comprises a substituted or unsubstituted C1-C3 group.

[0090] In some embodiments, the organometallic precursor or organometallic compound includes secondary hexyltri(dimethylamino)tin, tert-hexyltri(dimethylamino)tin, isohexyltri(dimethylamino)tin, n-hexyltri(dimethylamino)tin, secondary amyltri(dimethylamino)tin, tert-amyltri(dimethylamino)tin, isopentyltri(dimethylamino)tin, n-amyltri(dimethylamino)tin, secondary butyltri(dimethylamino)tin, tert-butyltri(dimethylamino)tin, isobutyltri(dimethylamino)tin, n-butyltri(dimethylamino)tin, isopropyltri(dimethylamino)tin, n-propyltri(dimethylamino)tin, In some embodiments, the organometallic precursor or organometallic compound is fluorinated. In some embodiments, the boiling point of the organometallic precursor or compound is less than about 200°C.

[0091] In some embodiments, the first compound or the first precursor comprises one or more unsaturated bonds that can coordinate with functional groups (eg, hydroxyl groups) on the surface of the substrate or the intermediate underlayer to improve adhesion of the photoresist layer to the substrate or the underlayer.

[0092] In some embodiments, the second precursor or second compound is one or more selected from amines, boranes, and phosphines. In some embodiments, the amine has the formula N p H n X m , wherein 0≤n≤3, 0≤m≤3, n+m=3 when p is 1, and n+m=4 when p is 2, and each X is independently a halogen selected from F, Cl, Br and I. In some embodiments, the borane has the formula B p H n X m , wherein 0≤n≤3, 0≤m≤3, when p is 1, n+m=3, and when p is 2, n+m=4, and each X is independently a halogen selected from F, Cl, Br and I. In some embodiments, the phosphine has the formula P p H n X m , wherein 0≤n≤3, 0≤m≤3, when p is 1, n+m=3, or when p is 2, n+m=4, and each X is independently a halogen selected from F, Cl, Br and I.

[0093] In some embodiments, the second precursor or compound is ammonia or hydrazine. The reaction product of ammonia or hydrazine with the organometallic precursor or compound can form hydrogen bonds, which increase the boiling point of the reaction product and prevent the emission of metal photoresist materials, thereby preventing metal contamination. Hydrogen bonds can also help prevent moisture from affecting the quality of the photoresist layer.

[0094] In some embodiments, the operation S110 of depositing the photoresist composition is performed by a vapor deposition operation. In some embodiments, the vapor deposition operation includes atomic layer deposition (ALD) or chemical vapor deposition (CVD). In some embodiments, ALD includes plasma enhanced atomic layer deposition (PE-ALD), and CVD includes plasma enhanced chemical vapor deposition (PE-CVD), metal organic chemical vapor deposition (MO-CVD); atmospheric pressure chemical vapor deposition (AP-CVD) and low pressure chemical vapor deposition (LP-CVD).

[0095] Depositing the photoresist layer includes combining a first compound or a first precursor with a second compound or a second precursor in a vapor state to form a photoresist composition. In some embodiments, the first compound or a first precursor and the second compound or a second precursor of the photoresist composition are introduced into the deposition chamber (CVD chamber) at about the same time. In some embodiments, the first compound or a first precursor and the second compound or a second precursor are introduced into the deposition chamber (ALD chamber) in an alternating manner, that is, the first compound or a precursor, then the second compound or a precursor, and then the first compound or a precursor is introduced alternately and repeatedly, and then the second compound or a precursor is introduced.

[0096] In some embodiments, during the deposition operation, the temperature of the deposition chamber is in the range of about 30°C to about 400°C, and in other embodiments, between about 50°C to about 250°C. In some embodiments, during the deposition operation, the pressure in the deposition chamber is in the range of about 5mTorr to about 100Torr, and in other embodiments, in the range of about 100mTorr to about 10Torr. In some embodiments, the plasma power is less than about 1000W. In some embodiments, the plasma power is in the range of about 100W to about 900W. In some embodiments, the flow rate of the first compound or precursor and the second compound or precursor is in the range of about 100sccm to about 1000sccm. In some embodiments, the ratio of the flow rate of the organometallic compound precursor to the second compound or precursor is about 1:1 to about 1:5. In some embodiments, at operating parameters outside the above ranges, unsatisfactory photoresist layers result. In some embodiments, the formation of the photoresist layer occurs in a single chamber (single pot layer formation).

[0097] In a CVD process according to some embodiments of the present disclosure, two or more gas streams of an organometallic precursor and a second precursor are introduced into a deposition chamber of a CVD apparatus in separate inlet paths, where they mix and react in the gas phase to form a reaction product. In some embodiments, separate injection inlets or dual boost nozzles are used to introduce each stream. The deposition apparatus is configured so that the streams of the organometallic precursor and the second precursor mix in the chamber, thereby reacting the organometallic precursor and the second precursor to form a reaction product. Without limiting the mechanism, function or utility of the present disclosure, it is believed that the molecular weight of the product from the gas phase reaction becomes larger and is then condensed or otherwise deposited on the substrate.

[0098] In some embodiments, an ALD process is used to deposit a photoresist layer. During ALD, a layer is grown on a substrate by exposing the surface of the substrate to alternating gaseous compounds (or precursors). In contrast to CVD, the precursors are introduced as a series of sequential, non-overlapping pulses. In each of these pulses, the precursor molecules react with the surface in a self-limiting manner, so that the reaction terminates once all reactive sites on the surface are consumed. Therefore, after a single exposure to all precursors (the so-called ALD cycle), the maximum amount of material deposited on the surface depends on the nature of the interaction of the precursors with the surface.

[0099] In one embodiment of the ALD process, in the first half of the reaction, the organometallic precursor is pulsed to deliver the metal-containing precursor to the surface of the substrate 10. In some embodiments, the organometallic precursor reacts with a suitable species below (e.g., OH or NH functional groups on the substrate surface) to form a new self-saturated surface. In some embodiments, excess unused reactants and reaction byproducts are removed by vacuuming downward and / or by flowing an inert purge gas. Then, in some embodiments, a second precursor such as ammonia (NH3) is pulsed into the deposition chamber. NH3 reacts with the organometallic precursor on the substrate to obtain a reaction product photoresist on the substrate surface. The second precursor also forms a self-saturated bond with the reactive species below to provide another self-limiting and saturated second half reaction. In some embodiments, a second purge is performed to remove unused reactants and reaction byproducts. The pulses of the first and second precursors are alternately performed with the purge operation in the middle until the desired thickness of the photoresist layer 15 is obtained.

[0100] In some embodiments, the photoresist layer 15 is formed to a thickness of about 5 nm to about 50 nm, and in other embodiments, to a thickness of about 10 nm to about 30 nm. Those of ordinary skill in the art will recognize that other ranges of thickness within the above-defined range are expected and within the present disclosure. Non-contact methods using X-ray reflectivity and / or ellipsometry can be used to evaluate the thickness based on the optical properties of the photoresist layer. The thickness of the photoresist layer is relatively uniform to facilitate processing. In some embodiments, the thickness variation of the coating differs from the average coating thickness by no more than ± 25%, and in other embodiments, the photoresist layer thickness differs from the average photoresist layer thickness by no more than ± 10%. In some embodiments, such as high uniformity coatings on larger substrates, the uniformity of the photoresist layer can be evaluated with a 1 cm edge exclusion, that is, the layer uniformity of the coating portion within 1 cm of the edge is not evaluated. Those of ordinary skill in the art will recognize that other ranges within the above-defined range are expected and within the present disclosure.

[0101] In some embodiments, the first compound or precursor and the second compound or precursor are delivered to the deposition chamber along with a carrier gas. The carrier gas, purge gas, deposition gas or other process gas may include nitrogen, hydrogen, argon, neon, helium or a combination thereof.

[0102] According to some embodiments of the present disclosure, the resist layer deposition apparatus 200 is Figure 8 . In some embodiments, the deposition apparatus 200 is an ALD or CVD apparatus. The deposition apparatus 200 includes a vacuum chamber 205. A substrate support table 210 in the vacuum chamber 205 supports a substrate 10 such as a silicon wafer. In some embodiments, the substrate support table 210 includes a heater. In some embodiments, a first precursor or compound gas supplier 220 and a carrier gas / purge gas supplier 225 are connected to an inlet 230 in the chamber via a gas line 235, and a second precursor or compound gas supplier 240 and a carrier gas / purge gas supplier 225 are connected to another inlet 230' in the chamber 230' via another gas line 235'. The chamber is evacuated, and excess reactants and reaction byproducts are removed via an outlet 250 and an exhaust line 255 by a vacuum pump 245. In some embodiments, the flow rates or pulses of precursor gases and carrier / purge gases, the exhaust of excess reactants and reaction byproducts, the pressure within the vacuum chamber 205, and the temperature of the vacuum chamber 205 or the wafer support table 210 are controlled by a controller 260 configured to control each of these parameters.

[0103] In some embodiments, the organometallic compound comprises tin (Sn), antimony (Sb), bismuth (Bi), indium (In) and / or tellurium (Te) as metal components, but the present disclosure is not limited to these metals. In other embodiments, other 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 a combination thereof. These other metals can be used as a substitute or supplement for Sn, Sb, Bi, In and / or Te.

[0104] The specific metal used can significantly affect the absorption of radiation. Therefore, the metal composition can be selected based on the desired radiation and absorption cross section. Tin, antimony, bismuth, tellurium and indium can strongly absorb extreme ultraviolet light at 13.5nm. Hafnium provides good electron beam absorption and extreme ultraviolet radiation absorption. Metal compositions containing titanium, vanadium, molybdenum or tungsten have strong absorption at longer wavelengths to provide, for example, sensitivity to ultraviolet light at a wavelength of 248nm.

[0105] In some embodiments, ALD or CVD deposition parameters are varied during a deposition operation to form a photoresist layer having a density gradient. In some embodiments, the density gradient photoresist layer reduces defects such as scum and bridging, and improves line width roughness (LWR) and line edge roughness (LER).

[0106] Fig. 9 The reactions that components of a photoresist composition according to one embodiment of the present disclosure undergo as a result of exposure to actinic radiation and heat are shown. Fig. 9 2 shows an exemplary chemical structure of a photoresist layer (PR) at various stages of a photoresist patterning method according to an embodiment of the present disclosure. Fig. 9 As shown, the photoresist composition includes an organic metal compound (e.g., SnX2R2), and a second compound, such as ammonia (NH3). When the organic metal compound and ammonia are combined, the organic metal compound reacts with some ammonia in the gas phase to form a reaction product having an amine group connected to the metal (Sn) of the organic metal compound. The amine group in the deposited photoresist layer has a hydrogen bond, which can substantially increase the boiling point of the deposited photoresist layer and prevent the degassing of the metal-containing photoresist material, thereby preventing the metal in the metal-containing photoresist from contaminating the deposition chamber and semiconductor device processing equipment. In the metal-containing photoresist. In addition, the hydrogen bond of the amine group can control the effect of moisture on the quality of the photoresist layer.

[0107] When subsequently exposed to EUV radiation using a mask, the organometallic compound absorbs the EUV radiation and one or more organic R groups are cleaved from the organometallic compound, thereby forming an amide metal compound in the radiation exposed areas. Then, in some embodiments, when a post-exposure bake (PEB) is performed, the amide metal compound is cross-linked through the amine groups, such as Fig. 9 In some embodiments, the metal amide compound is partially crosslinked due to exposure to extreme ultraviolet radiation. The selectively exposed photoresist is then developed, and the crosslinked radiation-exposed pattern is retained on the substrate while the unexposed radiation areas are removed during development.

[0108] In some embodiments, before forming the multi-layer photoresist layer, a layer to be patterned (target layer) 60 is disposed on a substrate, such as Fig.10 As shown. In some embodiments, the layer 60 to be patterned is a metallization layer or a dielectric layer disposed above the metallization layer, such as a passivation layer. In embodiments in which the layer 60 to be patterned is a metallization layer, the layer 60 to be patterned is formed of a conductive material using a metallization process and a metal deposition technique including chemical vapor deposition, atomic layer deposition, and physical vapor deposition (sputtering). Similarly, if the layer 60 to be patterned is a dielectric layer, the layer 60 to be patterned is formed by a dielectric layer formation technique including thermal oxidation, chemical vapor deposition, atomic layer deposition, and physical vapor deposition.

[0109] The photoresist layer 15 is then selectively exposed to actinic radiation 45 to form exposed areas 50 and unexposed areas 52 in the photoresist layer, such as Fig.11A and 11B As stated above, and herewith Figure 3A and 3B As explained herein, in some embodiments, the photoresist is a negative photoresist.

[0110] like Fig. 12A As shown, the unexposed photoresist areas 52 are developed by dispensing developer 57 from a dispenser 62, or by a dry developing operation, such as Fig. 12B As shown, a photoresist pattern 55 is formed to develop the unexposed photoresist region 52, as shown in FIG. Fig.13 The development operation is similar to that described in the present invention. Figure 4A , 4B and 5.

[0111] Then, if Fig.14 As shown, an etching operation is used to transfer the pattern 55 in the photoresist layer 15 to the layer 60 to be patterned, and the photoresist layer is removed, as shown in FIG. Figure 6As explained, a pattern 55" is thereby formed in the layer 60 to be patterned.

[0112] In some embodiments, Fig.15 As shown, the photoresist layer 15 is exposed to infrared, visible, or near-ultraviolet radiation 110 prior to selectively or pattern-by-pattern exposure of the photoresist layer to reduce or inhibit outgassing of the photoresist layer. The exposure to infrared, visible, or near-ultraviolet radiation is at a lower dose than the subsequent pattern-by-pattern exposure. In some embodiments, exposure to infrared, visible, or near-ultraviolet radiation can increase the density of the film and, in some embodiments, can reduce problems caused by moisture. In some embodiments, the photoresist layer is heat treated prior to selective or pattern-by-pattern exposure to increase the density of the photoresist layer. In some embodiments, the heat treatment includes heating the photoresist layer to a temperature of about 40° C. to 120° C. for about 10 seconds to about 10 minutes. Then, as described herein with reference to Figure 3A-6 and Figure 11A-14 The photoresist layer and substrate are processed as discussed above.

[0113] In some embodiments, Fig.16A As shown, the photoresist layer 15 includes an organic metal compound or precursor that includes one or more unsaturated bonds that can coordinate with the functional groups of the underlying substrate 10. Fig. 16B As shown, the deposited photoresist (PR) contains unsaturated bonds at uncoordinated positions. When the photoresist layer 15 is heated, the functional groups (e.g., hydroxyl groups) on the surface of the substrate 10 or the intermediate layer react with the unsaturated bonds and chemically bond the photoresist layer 15 to the substrate 10 or the intermediate layer, thereby improving the adhesion of the photoresist to the substrate. Then, as described herein with reference to Figure 3A-6 and Figure 11A-14 As discussed above, the photoresist layer and substrate are processed. In some embodiments, the substrate is a silicon substrate, such as a silicon wafer or a silicon layer.

[0114] In some embodiments, Fig.17As shown, before selectively or pattern-by-pattern exposing the resist layer 15 or crosslinking the resist layer 15, a capping layer 130 is applied to the resist layer. In some embodiments, the capping layer 130 is a non-metallic layer (e.g., silicon oxide or silicon nitride), or in other embodiments, a polymer layer. In some embodiments, the capping layer 130 is deposited by atomic layer deposition, chemical vapor deposition, or spin coating. In some embodiments, the capping layer 130 is deposited in the same chamber as the photoresist layer. In some embodiments, the capping layer 130 helps prevent resist degassing or metal contamination. Moreover, the capping layer 130 can help prevent moisture from harmfully affecting the photoresist layer. In some embodiments, the thickness of the capping layer is about 0.5nm to about 10nm. In other embodiments, the thickness of the capping layer is in the range of about 1nm to about 5nm. In some embodiments, the thickness below 0.5nm is too thin to effectively inhibit the effect of resist degassing and moisture on the resist layer, and the thickness above 10nm does not provide any additional benefits compared to the thickness of 10nm. Then, as referenced in this article Figure 3A-6 and Figure 11A-14 The photoresist layer and substrate are processed as discussed. In some embodiments, the capping layer 130 is removed before, during, or after the development operation. In some embodiments, the capping layer is removed prior to pattern-wise exposure.

[0115] In some embodiments, before the photoresist layer is formed on the substrate, the surface of the substrate is treated with hexamethyldisilazane (HMDS). Fig.18As shown, before forming the resist layer 15, an amorphous carbon-containing lower layer 115 (or simply referred to as "lower layer") is formed above the substrate. In some embodiments, the lower layer 115 reduces the harmful effects of moisture, and in some embodiments, the lower layer 115 improves the adhesion of the photoresist layer 15 to the substrate 10. In some embodiments, the amorphous carbon lower layer 115 is a carbon-based polymer layer. In some embodiments, the lower layer 115 is a layer containing amorphous carbon formed by chemical vapor deposition. In some embodiments, the lower layer 115 is deposited by a variety of techniques, such as by plasma-induced polymerization of unsaturated monomer precursors (e.g., ethylene, propylene, acetylene, or any other volatile hydrocarbon-based precursors). In some embodiments, the thickness of the lower layer 115 is about 0.5nm to about 10nm. In other embodiments, the thickness of the lower layer 115 is in the range of about 1nm to about 5nm. In some embodiments, the lower layer 115 improves the adhesion of the photoresist layer 15 to the surface of the substrate 10. In some embodiments, a thickness below 0.5 nm is too thin to effectively reduce the effects of moisture or improve the adhesion of the photoresist to the substrate 10, and a thickness above 10 nm does not provide any additional benefit compared to a thickness of 10 nm. Figure 3A-6 and Figure 11A-13 The photoresist layer and substrate are processed as discussed above. In some embodiments, the exposed portions of the underlying layer 115 are removed by etching.

[0116] In some embodiments, before selectively exposing or pattern-wise exposing the resist layer 15 or cross-linking the resist layer 15 to form the organosilane layer 120, an organosilane is applied to the resist layer, such as Figures 19A-19C In some embodiments, the organosilane top layer helps prevent resist outgassing or metal contamination. Furthermore, the top layer can help prevent moisture from detrimentally affecting the photoresist layer. Fig.19B yes Fig.19A Detailed view of the resist layer 15 showing an organosilane Y combined with an organometallic precursor or compound. The organosilane Y can be any suitable organosilane. In some embodiments, the organosilane is one or more selected from the group consisting of trisilylamine, 1,3,5-trisilacyclohexane, 1,3,5-trisilapentane, bis(diethylamino)silane, bis(tert-butylamino)silane, dichlorosilane, dibromosilane, diiodosilane, and disilane. In some embodiments, the organosilane is deposited by atomic layer deposition or chemical vapor deposition. Fig.19CAn example of a reaction between an organosilane and a resist layer is shown in FIG. An organic silane (organosilane) is deposited over the resist layer, and the organosilane coordinates with the organometallic in the resist layer. In some embodiments, in the same chamber, the organosilane is deposited on the top surface of the photoresist layer. Then, as described herein with reference to Figure 3A-6 and Figure 11A-14 The photoresist layer and substrate are processed as discussed. In some embodiments, the organosilane layer 120 is removed during or after the development operation.

[0117] Other embodiments include other operations before, during, or after the above operations. In some embodiments, the disclosed method includes forming a fin field effect transistor (FinFET) structure. In some embodiments, a plurality of active fins are formed on a semiconductor substrate. Such an embodiment further includes etching the substrate through the openings of the patterned 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; epitaxially growing or recessing the STI features to form a fin-shaped active area. In some embodiments, one or more gate electrodes are formed on the substrate. Some embodiments include forming gate spacers, doped source / drain regions, contacts for gate / source / drain features, and the like. In other embodiments, the target pattern is formed as a metal line in a multilayer interconnect structure. For example, the metal line can be formed in an interlayer dielectric (ILD) layer of the substrate, which has been etched to form a plurality of trenches. The trenches may be filled with a conductive material, such as a metal; and a process such as chemical mechanical planarization (CMP) may be used to polish the conductive material to expose the patterned ILD layer, thereby forming metal lines in the ILD layer. The above are non-limiting examples of devices / structures that may be manufactured and / or improved using the methods described herein.

[0118] 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 present disclosure.

[0119] Compared with solvent-based resists, the semiconductor formation method and resist patterning method according to the present disclosure provide improved resist material use efficiency and reduce the use of potentially toxic organic solvents. Embodiments of the present disclosure provide a uniform photoresist film deposited on the surface of a semiconductor substrate. In some embodiments, since the photoresist is not solvent-based, toxic organic solvents can be substantially eliminated from the photoresist patterning process, and dry development can be performed without using solvent-based developers. In some embodiments, metals in metal-containing photoresists are prevented from contaminating deposition chambers and semiconductor substrate processing equipment. By the method according to an embodiment of the present disclosure, the problem of photoresist moisture sensitivity is prevented. The embodiments of the present disclosure provide improved pattern resolution. In addition, by the single-pot deposition method according to an embodiment of the present disclosure, improved semiconductor device manufacturing efficiency is provided.

[0120] The dry patterning techniques disclosed herein can provide various benefits relative to wet patterning. For example, the dry deposition techniques described herein can be used to deposit thinner and more defect-free films than coating using spin coating techniques, and the exact thickness of the deposited film can be adjusted and controlled by increasing or decreasing the length or sequence of the deposition steps. Therefore, dry processes can provide more adjustability and give further critical dimension (CD) control and scum removal. Dry development can improve performance by preventing line collapse due to surface tension in wet development and increase production throughput by avoiding wet development tracks. Embodiments of the present disclosure improve line width roughness and the distinction between exposed and unexposed portions of the photoresist.

[0121] One embodiment of the present disclosure is a method of manufacturing 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 is a material of formula M a R b X cAn organometallic precursor, wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce or Lu; R is a substituted or unsubstituted alkyl, alkenyl or carboxylate group; X is a halogen 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 or a phosphine. Forming a photoresist includes: depositing a photoresist material over a substrate. The photoresist layer is selectively exposed to actinic radiation to form a latent pattern, and the latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern. In one embodiment, the actinic radiation is extreme ultraviolet radiation. In one embodiment, the method includes baking the photoresist layer after selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before developing the latent pattern. In one embodiment, an alkyl, alkenyl or carboxylate group is substituted with one or more fluorine groups. In one embodiment, a sulfonate group is substituted with one or more amine groups. In one embodiment, a photoresist material is deposited on a substrate by atomic layer deposition (ALD) or chemical vapor deposition (CVD). In one embodiment, the method includes exposing the photoresist layer to infrared, visible light or near-ultraviolet radiation before selectively exposing the photoresist layer to actinic radiation. In one embodiment, the method includes forming a layer containing amorphous carbon above the substrate before forming the photoresist layer. In one embodiment, the method includes forming a carbon-based polymer layer above the substrate before forming the photoresist layer. In one embodiment, the method includes applying an organosilane 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 includes forming silicon oxide or silicon nitride above the photoresist layer before selectively exposing the photoresist layer.

[0122] Another embodiment of the present disclosure is a method for manufacturing a semiconductor device, comprising: depositing a photoresist composition on a substrate surface by atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form a photoresist layer, the photoresist composition having a first compound and a second compound. Depositing the photoresist layer comprises combining the first compound and the second compound in a vapor state to form a photoresist composition, wherein the first compound is at least one of the following: secondary hexyl tris (dimethylamino) tin, tert-hexyl tris (dimethylamino) tin, isohexyl tris (dimethylamino) tin, n-hexyl tris (dimethylamino) tin, secondary amyl tris (dimethylamino) tin, tert-amyl tris (dimethylamino) tin, isopentyl tris (dimethylamino) tin, n-amyl tris (dimethylamino) tin, secondary butyl tris (dimethylamino) tin, tert-butyl tris (dimethylamino) tin, isobutyl tris (dimethylamino) tin, n-butyl tris (dimethylamino) tin The photoresist layer is selectively exposed to actinic radiation to form a latent pattern. The latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern that exposes a portion of the substrate surface. The portion of the substrate exposed by the development is removed. In one embodiment, removing the portion of the substrate exposed by the development includes etching the substrate. In one embodiment, the actinic radiation is extreme ultraviolet radiation. In one embodiment, the method includes heating the photoresist layer at a temperature in the range of 100° C. to 200° C. after selectively exposing the photoresist layer to actinic radiation to form the latent pattern and before developing the latent pattern. In one embodiment, the first compound is substituted with one or more fluorine groups. In one embodiment, the developer is a dry developer. In one embodiment, the method includes exposing the photoresist layer to infrared, visible light, or near ultraviolet radiation before selectively exposing the photoresist layer to actinic radiation. In one embodiment, the method includes 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 organosilane to the photoresist layer prior to selectively exposing the photoresist layer to actinic radiation. In one embodiment, the amine is ammonia or hydrazine.In one embodiment, the method includes forming silicon oxide or silicon nitride over the photoresist layer before selectively exposing the photoresist layer.

[0123] Another embodiment of the present disclosure is a method for manufacturing a semiconductor device, the method including introducing a first compound and a second compound into a chamber simultaneously to form a composition of the first compound and the second compound. The composition of the first compound and the second compound is deposited on 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 amines, boranes, phosphines, and combinations thereof. The layer of the composition is exposed to actinic radiation pattern by pattern to form a latent pattern, and the layer of the composition exposed pattern by pattern is developed to form a layer of a patterned composition. In one embodiment, the amine, borane, or phosphine contains a halogen substituent. In one embodiment, the method includes exposing the layer of the composition to infrared, visible light, or near-ultraviolet radiation before exposing the layer of the composition pattern by pattern to actinic radiation. In one embodiment, the method includes forming a polymer layer above the substrate before depositing the composition. In one embodiment, the method includes applying an organosilane to the layer of the composition before selectively exposing the layer of the composition to actinic radiation. In one embodiment, the actinic radiation is extreme ultraviolet radiation. In one embodiment, the method includes heating the layer of the composition at a temperature ranging from 100° C. to 200° C. after pattern-wise exposing the layer of the composition to actinic radiation to form a latent pattern and before developing the latent pattern. In one embodiment, the method includes removing the portion of the substrate exposed by the developed surface. In one embodiment, removing the portion of the substrate exposed by the development includes performing a dry development operation on the substrate. In one embodiment, the development is a dry development operation. In one embodiment, the amine is ammonia or hydrazine. In one embodiment, the method includes forming silicon oxide or silicon nitride over the layer of the composition before selectively exposing the layer of the composition.

[0124] Another embodiment of the present disclosure is a method for patterning a resist layer, comprising depositing a resist layer over a substrate surface by atomic layer deposition (ALD) or chemical vapor deposition (CVD). The resist layer includes a reaction product of a silicon-free organic metal compound and a compound selected from amines, boranes, and phosphines. The resist layer is cross-linked pattern by pattern to form a latent pattern in the resist layer. The latent pattern is developed by applying a developer to the cross-linked resist layer pattern by pattern to form a pattern 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 organic metal compound includes a metal selected from Sn, Bi, Sb, In, and Te. In one embodiment, the organic metal compound includes a substituted or unsubstituted alkyl, alkenyl, or carboxylate group. In one embodiment, the organic metal compound includes a halogen or sulfonate group. In one embodiment, the sulfonate group is substituted by one or more amine groups. In one embodiment, the amine, borane, or phosphine contains a halogen substituent. In one embodiment, pattern-by-pattern crosslinking the resist layer comprises exposing the resist layer to extreme ultraviolet radiation gradually and heating the pattern-by-pattern exposed resist layer. In one embodiment, the pattern-by-pattern exposed resist layer is heated at a temperature in the range of 100° C. to 200° C. In one embodiment, the method comprises exposing the resist layer to infrared, visible light, or near ultraviolet radiation before pattern-by-pattern crosslinking the resist layer. In one embodiment, the amine is ammonia or hydrazine. In one embodiment, the method comprises forming silicon oxide or silicon nitride over the resist layer before selectively pattern-by-pattern crosslinking the photoresist layer.

[0125] Another embodiment of the present disclosure is a method of forming a patterned layer over a substrate surface, comprising depositing a reaction product of a vapor phase organometallic compound and a second vapor phase compound over the substrate to form a resist layer. The organometallic compound has a molecular formula of: M a R b X c, wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce or Lu; R is a substituted or unsubstituted alkyl, alkenyl or carboxylate group; X is a halogen or sulfonate group; and 1≤a≤2, b≥1, c≥1, and b+c≤5; and the second gas phase compound is selected from amines, boranes, phosphines and combinations thereof. The resist layer is crosslinked pattern by pattern to form a latent pattern in the resist layer. The latent pattern is developed by applying a developer to the crosslinked resist layer pattern by pattern to form a pattern exposing a portion of the substrate surface. In one embodiment, X is a sulfonate group substituted with one or more amine groups. In one embodiment, the amine, borane or phosphine contains a halogen substituent. In one embodiment, crosslinking the resist layer pattern by pattern includes exposing the resist layer pattern by pattern to extreme ultraviolet radiation and heating the exposed resist layer pattern by pattern. In one embodiment, the resist layer cross-linked pattern by pattern is heated at a temperature in the range of 100°C to 200°C. In one embodiment, the method includes removing portions of the substrate exposed by development. In one embodiment, the method includes heating the resist layer at a temperature in the range of 40°C to 120°C before cross-linking the resist layer pattern by pattern. In one embodiment, the method includes forming an amorphous carbon layer over the substrate before forming the resist layer. In one embodiment, the amorphous carbon layer is a polymer layer. In one embodiment, the method includes applying an organosilane to the resist layer before cross-linking the resist layer pattern by pattern. In one embodiment, the amine is ammonia or hydrazine. In one embodiment, the method includes forming silicon oxide or silicon nitride on the resist layer before cross-linking the photoresist layer pattern by pattern.

[0126] Another embodiment of the present disclosure is a method for patterning a photoresist layer, comprising depositing 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 amines, boranes, phosphines, and combinations thereof. The photoresist layer is selectively exposed to actinic radiation to form a latent pattern in the photoresist layer. Portions of the photoresist layer that are not exposed to actinic radiation are removed to form a pattern of the remaining portion of the photoresist layer that is exposed to actinic radiation during the selective exposure of the photoresist layer. In one embodiment, the method comprises removing portions of the substrate exposed by removing portions of the photoresist layer. In one embodiment, removing portions of the substrate comprises dry etching the substrate. In one embodiment, removing portions of the photoresist layer comprises applying plasma to the photoresist layer. In one embodiment, the vapor deposition operation comprises atomic layer deposition or chemical vapor deposition. In one embodiment, the amine, borane, or phosphine comprises a halogen substituent. In one embodiment, the actinic radiation is extreme ultraviolet radiation. In one embodiment, the method includes heating the photoresist layer at a temperature in the range of 100°C to 200°C after selectively exposing the photoresist layer to actinic radiation. In one embodiment, the method includes exposing the photoresist layer to infrared, visible light, or near ultraviolet radiation before selectively exposing the photoresist layer to actinic radiation. In one embodiment, the method includes heating the photoresist layer at a temperature in the range of 40°C to 120°C before selectively exposing the photoresist layer to actinic radiation. In one embodiment, the amine is ammonia or hydrazine. In one embodiment, the method includes forming silicon oxide or silicon nitride over the photoresist layer before selectively exposing the photoresist layer.

[0127] Some exemplary implementations are described below:

[0128] Embodiment 1. A method for manufacturing a semiconductor device, comprising:

[0129] A photoresist layer is formed over the substrate, comprising:

[0130] combining a first precursor and a second precursor in a vapor state to form a photoresist material,

[0131] Wherein the first precursor is a compound having the formula M a R b X c Organometallics:

[0132] wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce or Lu,

[0133] R is a substituted or unsubstituted alkyl, alkenyl or carboxylate group,

[0134] X is a halogen or a sulfonate group, and

[0135] 1≤a≤2, b≥1, c≥1, and b+c≤5, and

[0136] The second precursor is at least one of an amine, a borane, or a phosphine; and

[0137] depositing the photoresist over a substrate;

[0138] selectively exposing the photoresist layer to actinic radiation to form a latent pattern; and

[0139] The latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern.

[0140] Embodiment 2. The method of embodiment 1, wherein the actinic radiation is extreme ultraviolet radiation.

[0141] Embodiment 3. The method of embodiment 1 further comprising baking the photoresist layer after selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before developing the latent pattern.

[0142] Embodiment 4. The method of embodiment 1, wherein the alkyl, alkenyl, or carboxylate group is substituted with one or more fluoro groups.

[0143] Embodiment 5. The method of embodiment 1, wherein the sulfonate group is substituted with one or more amine groups.

[0144] Embodiment 6. The method of embodiment 1, wherein the photoresist material is deposited over the substrate by atomic layer deposition (ALD) or chemical vapor deposition (CVD).

[0145] Embodiment 7. The method of embodiment 1 further comprising exposing the photoresist layer to infrared, visible light, or near ultraviolet radiation before selectively exposing the photoresist layer to actinic radiation.

[0146] Embodiment 8. The method of embodiment 1, further comprising forming an amorphous carbon-containing layer over the substrate before forming the photoresist layer.

[0147] Embodiment 9. The method of embodiment 1, further comprising forming a carbon-based polymer layer over the substrate before forming the photoresist layer.

[0148] Embodiment 10. The method of embodiment 1, further comprising applying an organosilane to the photoresist layer prior to selectively exposing the photoresist layer to actinic radiation.

[0149] Embodiment 11. A method for manufacturing a semiconductor device, comprising:

[0150] depositing a photoresist composition on a substrate surface by atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form a photoresist layer, wherein the photoresist composition includes a first compound and a second compound,

[0151] The deposited photoresist composition comprises:

[0152] combining the first compound and the second compound in a vapor state to form a photoresist composition,

[0153] wherein the first compound is at least one of the following: secondary hexyl tris(dimethylamino)tin, tert-hexyl tris(dimethylamino)tin, isohexyl tris(dimethylamino)tin, n-hexyl tris(dimethylamino)tin, secondary amyl tris(dimethylamino)tin, tert-amyl tris(dimethylamino)tin, isopentyl tris(dimethylamino)tin, n-amyl tris(dimethylamino)tin, secondary butyl tris(dimethylamino)tin, tert-butyl tris(dimethylamino)tin, isobutyl tris(dimethylamino)tin, n-butyl tris(dimethylamino)tin, secondary butyl tris(dimethylamino)tin, isopropyl tris(dimethylamino)tin, n-propyltri(diethylamino)tin and similar alkyltri(tert-butoxy)tin compounds, including sec-hexyltri(tert-butoxy)tin, tert-hexyltri(tert-butoxy)tin, isohexyltri(tert-butoxy)tin, n-hexyltri(tert-butoxy)tin, sec-amyltri(tert-butoxy)tin, tert-amyltri(tert-butoxy)tin, isopentyltri(tert-butoxy)tin, n-amyltri(tert-butoxy)tin, tert-butyltri(tert-butoxy)tin, isobutyltri(butoxy)tin, n-butyltri(butoxy)tin, sec-butyltri(butoxy)tin, isopropyltri(dimethylamino)tin or n-propyltri(butoxy)tin, and

[0154] The second compound is at least one of an amine, a borane, or a phosphine, and

[0155] selectively exposing the photoresist layer to actinic radiation to form a latent pattern;

[0156] developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern exposing a portion of the substrate surface; and

[0157] The portions of the substrate exposed by the development are removed.

[0158] Embodiment 12. The method of embodiment 11, wherein removing the portion of the substrate exposed by the developing comprises etching the substrate.

[0159] Embodiment 13. The method of embodiment 11, wherein the actinic radiation is extreme ultraviolet radiation.

[0160] Embodiment 14. The method of embodiment 11 further comprises heating the photoresist layer at a temperature ranging from 100° C. to 200° C. after selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before developing the latent pattern.

[0161] Embodiment 15. The method of embodiment 11, wherein the first compound is substituted with one or more fluoro groups.

[0162] Embodiment 16. A method of manufacturing a semiconductor device, comprising:

[0163] simultaneously introducing a first compound and a second compound into the chamber to form a composition of the first compound and the second compound;

[0164] depositing the composition of the first compound and the second compound on a substrate by chemical vapor deposition (CVD) to form a layer of the composition,

[0165] The first compound is an organic metal compound, and the second compound is selected from amines, boranes, phosphines and combinations thereof.

[0166] patternwise exposing the layer of the composition to actinic radiation to form a latent pattern; and

[0167] The pattern-wise exposed layer of the composition is developed to form a patterned layer of the composition.

[0168] Embodiment 17. The method of embodiment 16, wherein the amine, borane, or phosphine comprises a halogen substituent.

[0169] Embodiment 18. The method of embodiment 16, further comprising exposing the layer of the composition to infrared, visible light, or near ultraviolet radiation prior to patternwise exposing the layer of the composition to actinic radiation.

[0170] Embodiment 19. The method of embodiment 16, further comprising forming a polymer layer over the substrate before depositing the composition.

[0171] Embodiment 20. The method of embodiment 16, further comprising applying an organosilane to the layer of the composition prior to selectively exposing the layer of the composition to actinic radiation.

[0172] The features of several embodiments or examples are summarized above so that those skilled in the art can better understand the various aspects of the present disclosure. Those skilled in the art should understand that they can easily use the present disclosure as a basis for designing or modifying other processes and structures to carry out the same purposes and / or achieve the same advantages as the embodiments or examples introduced herein. Those skilled in the art should also recognize that such equivalent constructions do not depart from the spirit and scope of the present disclosure, and that they can make various changes, substitutions and modifications herein without departing from the spirit and scope of the present disclosure.

Claims

1. A method for manufacturing a semiconductor device, comprising: A photoresist layer is formed over the substrate, comprising: combining a first precursor and a second precursor in a vapor state to form a photoresist material, Wherein the first precursor is a compound having the formula M a R b X c Organometallics: wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, As, Y, La, Ce or Lu, R is a substituted or unsubstituted alkyl, alkenyl or carboxylate group, X is a halogen or sulfonate group, wherein X is a ligand, ion or other fragment that reacts with the second precursor, and 1≤a≤2, b≥1, c≥1, and b+c≤5, and The second precursor is at least one of an amine, a borane, or a phosphine; and depositing the photoresist over a substrate; selectively exposing the photoresist layer to actinic radiation to form a latent pattern, wherein the actinic radiation cleaves R from the photoresist material; After forming the latent pattern, baking the photoresist layer to crosslink the exposed photoresist layer; and After baking the photoresist layer, the latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern.

2. The method according to claim 1, wherein: The actinic radiation is extreme ultraviolet radiation.

3. The method according to claim 1, wherein the alkyl, alkenyl or carboxylate group is substituted with one or more fluorine groups.

4. The method according to claim 1, wherein the sulfonate groups are substituted with one or more amine groups.

5. The method according to claim 1, wherein: The photoresist material is deposited over the substrate by atomic layer deposition or chemical vapor deposition.

6. The method of claim 1, further comprising exposing the photoresist layer to infrared, visible light, or near ultraviolet radiation prior to selectively exposing the photoresist layer to actinic radiation. 7 . The method of claim 1 , further comprising forming an amorphous carbon-containing layer over the substrate before forming the photoresist layer. 8 . The method of claim 1 , further comprising forming a carbon-based polymer layer over the substrate before forming the photoresist layer.

9. The method of claim 1 further comprising applying an organosilane to the photoresist layer prior to selectively exposing the photoresist layer to actinic radiation.

10. A method for manufacturing a semiconductor device, comprising: depositing a photoresist composition on a substrate surface by atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form a photoresist layer, wherein the photoresist composition includes a first compound and a second compound, The deposited photoresist composition comprises: combining the first compound and the second compound in a vapor state to form a photoresist composition, wherein the first compound is at least one of the following: secondary hexyl tris(dimethylamino)tin, tert-hexyl tris(dimethylamino)tin, isohexyl tris(dimethylamino)tin, n-hexyl tris(dimethylamino)tin, secondary amyl tris(dimethylamino)tin, tert-amyl tris(dimethylamino)tin, isopentyl tris(dimethylamino)tin, n-amyl tris(dimethylamino)tin, secondary butyl tris(dimethylamino)tin, tert-butyl tris(dimethylamino)tin, isobutyl tris(dimethylamino)tin, n-butyl tris(dimethylamino)tin, secondary butyl tris(dimethylamino)tin, isopropyl tris(dimethylamino)tin, n-propyltri(diethylamino)tin and similar alkyltri(tert-butoxy)tin compounds, including sec-hexyltri(tert-butoxy)tin, tert-hexyltri(tert-butoxy)tin, isohexyltri(tert-butoxy)tin, n-hexyltri(tert-butoxy)tin, sec-amyltri(tert-butoxy)tin, tert-amyltri(tert-butoxy)tin, isopentyltri(tert-butoxy)tin, n-amyltri(tert-butoxy)tin, tert-butyltri(tert-butoxy)tin, isobutyltri(butoxy)tin, n-butyltri(butoxy)tin, sec-butyltri(butoxy)tin, isopropyltri(dimethylamino)tin or n-propyltri(butoxy)tin, and The second compound is at least one of an amine, a borane, or a phosphine, and selectively exposing the photoresist layer to actinic radiation to form a latent pattern; developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern exposing a portion of the substrate surface; and The portions of the substrate exposed by the development are removed.

11. The method according to claim 10, wherein: Removing the portion of the substrate exposed by the developing includes etching the substrate.

12. The method according to claim 10, wherein: The actinic radiation is extreme ultraviolet radiation.

13. The method of claim 10, further comprising heating the photoresist layer at a temperature ranging from 100°C to 200°C after selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before developing the latent pattern. The method of claim 10 , wherein the first compound is substituted with one or more fluoro groups.

15. A method for manufacturing a semiconductor device, comprising: simultaneously introducing a first compound and a second compound into the chamber to form a composition of the first compound and the second compound; depositing the composition of the first compound and the second compound on a substrate by chemical vapor deposition (CVD) to form a layer of the composition, Wherein the first compound is of formula M a R b X c of organometallic compounds, wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, As, Y, La, Ce or Lu, R is a substituted or unsubstituted alkyl, alkenyl or carboxylate group, X is a halogen or sulfonate group, wherein X is a ligand, ion or other fragment that reacts with the second precursor, and 1≤a≤2, b≥1, c≥1, and b+c≤5, The second compound is selected from amines, boranes, phosphines and combinations thereof; patternwise exposing the layer of the composition to actinic radiation to form a latent pattern, wherein the actinic radiation cleaves R from the photoresist material; After forming the latent pattern, baking the photoresist layer to crosslink the exposed photoresist layer; and After baking the photoresist layer, the pattern-wise exposed layer of the composition is developed to form a patterned layer of the composition.

16. The method according to claim 15, wherein: The amine, borane or phosphine comprises a halogen substituent.

17. The method of claim 15, further comprising exposing the layer of the composition to infrared, visible light, or near ultraviolet radiation prior to patternwise exposing the layer of the composition to actinic radiation.

18. The method of claim 15, further comprising forming a polymer layer over the substrate prior to depositing the composition.

19. The method of claim 15, further comprising applying an organosilane to the layer of the composition prior to selectively exposing the layer of the composition to actinic radiation.

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