Method for manufacturing semiconductor device

Abstract

The present disclosure relates to a method for manufacturing a semiconductor device. A method for manufacturing a semiconductor device includes: forming a photoresist layer on a substrate, including: combining a first precursor and a second precursor in a vapor state to form a photoresist material, and depositing the photoresist material on the substrate. A protective layer is formed on the photoresist layer. The photoresist layer is selectively exposed to actinic radiation through the protective layer to form a latent pattern in the photoresist layer. The protective layer is removed, 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 of manufacturing a semiconductor device. Background Art

[0002] As consumer devices become smaller in response to consumer demand, the size of the individual components of these devices must also decrease. The semiconductor devices that make up the main components of devices such as mobile phones, computer tablets, etc. have been compressed smaller and smaller, where the corresponding stress on the individual devices (such as transistors, resistors, capacitors, etc.) within the semiconductor devices will also 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 change, and the lack of change 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 has become increasingly tight. Therefore, 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 trend towards smaller and smaller components can be maintained. Summary of the invention

[0005] According to one embodiment of the present disclosure, a method for manufacturing a semiconductor device is provided, 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, and depositing the photoresist material over the substrate; forming a protective layer over the photoresist layer; selectively exposing the photoresist layer to actinic radiation through the protective layer to form a latent pattern in the photoresist layer; removing the protective layer; and developing the latent pattern to form a pattern by applying a developer to the selectively exposed photoresist layer.

[0006] According to another embodiment of the present disclosure, a method for manufacturing a semiconductor device is provided, comprising: depositing a photoresist composition over a substrate surface via atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form a photoresist layer, the photoresist composition comprising a first organic metal compound and a second compound; forming a protective layer comprising a polymer over the photoresist layer; selectively exposing the photoresist layer to actinic radiation through the protective layer to form a latent pattern; removing the protective layer; developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern exposing a portion of the substrate surface; and removing the portion of the substrate surface exposed by the development.

[0007] According to another embodiment of the present disclosure, a method for manufacturing a semiconductor device is provided, comprising: simultaneously introducing a first compound and a second compound into a 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 via chemical vapor deposition (CVD) to form a layer of the composition of the first compound and the second compound, wherein the first compound is an organic metal compound and the second compound is at least one of amine, borane, phosphine or water; forming a protective layer by coating a protective layer composition on the layer of the composition of the first compound and the second compound, the protective layer composition comprising a polymer and a solvent; exposing the layer of the composition of the first compound and the second compound to actinic radiation in a pattern through the protective layer to form a latent pattern in the layer of the composition of the first compound and the second compound; removing the protective layer; and developing the layer of the composition exposed in the pattern to form a patterned layer of the composition of the first compound and the second compound. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] The present disclosure will be best understood from the following detailed description when read in conjunction with the accompanying drawings. It should be noted that, in accordance with industry standard practice, various features are not drawn to scale and are only used for illustrative purposes. In fact, the size of various features may be arbitrarily increased or reduced for clarity of discussion.

[0009] Figure 1 A process flow for manufacturing a semiconductor device according to an embodiment of the present disclosure is shown.

[0010] Figure 2 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0011] Figure 3 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0012] Figure 4A and Figure 4B The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0013] Figure 5 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0014] Fig. 6A , Figure 6B and Figure 6C The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0015] Figure 7 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0016] Figure 8 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0017] Fig. 9A , Fig. 9B and Fig. 9C An organometallic precursor according to an embodiment of the present disclosure is shown.

[0018] Fig.10 A photoresist deposition apparatus according to some embodiments of the present disclosure is shown.

[0019] Fig.11 The reactions that a photoresist layer undergoes due to exposure to actinic radiation and heat according to an embodiment of the present disclosure are shown.

[0020] Fig.12 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0021] Fig.13 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0022] Fig.14A and Fig. 14B The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0023] Fig.15 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0024] Fig.16A , Fig. 16B and Fig. 16C The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0025] Fig.17 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0026] Fig.18 The process stages are shown in sequential operation according to an embodiment of the present disclosure. DETAILED DESCRIPTION

[0027] It should be understood that the following disclosure provides many different embodiments or examples for realizing 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 merely 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 depends on the process conditions and / or desired properties of the device. In addition, in the following description, forming a first feature on or above a second feature may include an embodiment in which the first feature and the second feature are formed in direct contact, and may also include an embodiment in which an additional feature may be 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 the purpose of simplicity and clarity, various features may be drawn arbitrarily in different proportions.

[0028] In addition, for ease of description, spatially relative terms such as "below," "beneath," "below," "above," "on," etc. may be used herein to describe the relationship of one element or feature to another (some) elements or features as shown in the figures. Spatially relative terms are intended to include different orientations of the device being used or operated in addition to the orientation shown in the figures. The device may be oriented in other ways (rotated 90 degrees or in other orientations), and the spatially relative descriptors used herein may be interpreted accordingly. In addition, the term "made of..." may refer to "including" or "comprising."

[0029] As the semiconductor industry moves into nanotechnology process nodes in pursuit of higher device density, higher performance and lower cost, there is a challenge to reduce semiconductor feature size. Extreme ultraviolet lithography (EUVL) has been developed to form smaller semiconductor device feature sizes and increase device density on semiconductor wafers. To improve EUVL, it is necessary to increase wafer exposure throughput. Wafer exposure throughput can be increased by increasing exposure power or increasing resist photospeed (sensitivity).

[0030] Metal-containing photoresists are used in extreme ultraviolet (EUV) lithography because metals have a high absorption capacity for EUV radiation and thus increase the resist exposure speed. However, metal-containing photoresist layers may outgas during processing, which may cause the quality of the photoresist layer to change over time and may cause contamination to semiconductor device processing chambers, handling equipment (e.g., front opening unified pods (FOUPs) and other semiconductor wafers), thereby negatively affecting lithography performance and increasing defects.

[0031] It is desirable to perform photoresist layer formation and patterning operations that substantially reduce or prevent metal contamination of processing chambers, substrate handling equipment, and other wafers from metals in the metal-containing photoresist.

[0032] In embodiments of the present disclosure, the above problems are solved by forming a protective layer over a metal-containing photoresist layer on a substrate. In addition, embodiments of the present disclosure include the formation of a solvent-free photoresist layer, thereby providing a more environmentally friendly process. Figure 1 FIG. 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 a surface of a substrate 10 or a layer to be patterned 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. In some embodiments, after the resist layer 15 is deposited, it then undergoes a first heating operation S120. In other embodiments, the metal-containing photoresist layer is formed by a spin coating method. In some embodiments, the resist layer is heated to a temperature between about 40° C. and about 150° C. for about 10 seconds to about 10 minutes.

[0033] After the optional first heating operation S120 or the resist deposition operation S110, in operation S130, a protective layer 20 is formed on the resist layer 15, such as Figure 3 As shown. In some embodiments, the protective layer 20 is formed on the resist layer 15 by a spin coating operation. In some embodiments, the protective layer 20 is then heated in a second heating operation S140 to remove the solvent or dry the protective layer. In some embodiments, the second heating operation S140 is performed at a temperature between about 40° C. and about 150° C. for about 10 seconds to about 10 minutes.

[0034] In operation S150, the resist layer 15 and the protective layer 20 are then selectively exposed to actinic radiation 45 / 97 (see Figure 4A and 4B). The resist layer 15 is exposed to actinic radiation 45 / 97 through the protective layer 20. In some embodiments, the actinic radiation 45 / 97 is not substantially absorbed by the protective layer 20. In some embodiments, the photoresist layer 15 is selectively or patterned exposed to ultraviolet radiation. In some embodiments, the ultraviolet radiation is deep ultraviolet radiation (DUV). In some embodiments, the ultraviolet radiation is extreme ultraviolet (EUV) radiation. In some embodiments, the resist layer 15 is selectively or patterned exposed to an electron beam. In some embodiments, the resist layer 15 is a photoresist layer that is photosensitive to actinic radiation 45 / 97, and the protective layer 20 is not a photoresist layer and is not photosensitive to actinic radiation 45 / 97. A photoresist layer according to the present disclosure is a layer that undergoes a chemical reaction upon absorption of actinic radiation, such that portions of the photoresist layer exposed to the actinic radiation change solubility in a developer compared to portions of the photoresist layer that are not exposed to the actinic radiation. A layer that is not sensitive to actinic radiation does not substantially undergo a chemical reaction upon exposure to actinic radiation that changes the solubility of the layer in the developer.

[0035] like Figure 4A As shown, in some embodiments, exposure radiation 45 passes through photomask 30 before irradiating photoresist layer 15. In some embodiments, photomask 30 has a pattern to be replicated in photoresist layer 15. In some embodiments, the pattern is formed by an opaque pattern 35 on photomask substrate 40. Opaque pattern 35 can be formed of a material that is opaque to ultraviolet radiation (e.g., chromium), while photomask substrate 40 is formed of a material that is transparent to ultraviolet radiation (e.g., fused silica).

[0036] In some embodiments, EUV lithography is used to perform selective or patterned exposure of the photoresist layer 15 to form exposed areas 50 and unexposed areas 52. In some embodiments, in the EUV lithography operation, a reflective photomask 65 is used to form a patterned exposure light, such as Figure 4B 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 cap layer 80 and an absorption layer 85 are formed on the reflective multilayer 75. A rear conductive layer 90 is formed on the back side of the low thermal expansion substrate 70. EUV radiation 95 is directed toward the reflective photomask 65 at an incident angle of about 6°. A portion 97 of the EUV radiation is reflected by the Si / Mo multilayer 75 toward the photoresist-coated substrate 10, while a portion of the EUV radiation that is incident on the absorption layer 85 is absorbed by the photomask. In some embodiments, additional optical elements (including reflectors) are located between the reflective photomask 65 and the photoresist-coated substrate 10.

[0037] In some embodiments, radiation exposure is performed by placing the photoresist coated substrate in a lithography tool. The lithography tool includes a photomask 30 / 65, optical elements, an exposure radiation source providing radiation 45 / 97 for exposure, and a movable stage for supporting and moving the substrate under the exposure radiation.

[0038] In some embodiments, optical elements (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 optical elements include one or more lenses, mirrors, filters, and combinations thereof to control the radiation 45 / 97 along its path.

[0039] 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 light (wavelength of 248 nm), ArF excimer laser light (wavelength of 193 nm), F2 excimer laser light (wavelength of 157 nm), or CO2 laser excited Sn plasma (extreme ultraviolet, wavelength of 13.5 nm).

[0040] The amount of electromagnetic radiation can be characterized by a fluence or dose, which is obtained by integrating the radiation flux during the exposure time. In some embodiments, a suitable radiation fluence ranges from about 1 mJ / cm 2 To about 150mJ / cm 2 In other embodiments, suitable radiation fluence ranges from about 2 mJ / cm 2 To about 100mJ / cm 2 , and in other embodiments, a suitable radiation fluence ranges from about 3 mJ / cm 2 To about 50mJ / cm 2 One of ordinary skill in the art will recognize that additional ranges of radiation flux within the explicit ranges described above are contemplated and within the scope of the present disclosure.

[0041] In some embodiments, selective or patterned exposure is performed by scanning an electron beam. With electron beam lithography, the electron beam generates secondary electrons that alter the irradiated material. High resolution can be achieved using electron beam lithography and metal-containing resists disclosed herein. The electron beam can be characterized by beam energy, and in some embodiments, suitable energies range from about 5V to about 200kV (kilovolts), while in other embodiments, suitable energies range from about 7.5V to about 100kV. In some embodiments, the close-range correction beam dose ranges from about 0.1μC / cm at 30kV.2 To about 5μC / cm 2 In other embodiments, the brachytherapy beam dose at 30 kV ranges from about 0.5 μC / cm 2 To about 1μC / cm 2 , and in other embodiments, the brachytherapy beam dose ranges from about 1 μC / cm at 30 kV. 2 To about 100μC / cm 2 One of ordinary skill in the art can calculate corresponding doses at other beam energies based on the teachings herein, and will recognize that additional ranges of electron beam properties within the explicit ranges above are contemplated and within the scope of the present disclosure.

[0042] The regions 50 in the resist layer exposed to radiation undergo a chemical reaction, thereby changing its sensitivity to removal in the subsequent development operation S175. In some embodiments, the portions 50 in the resist layer exposed to radiation undergo a reaction that makes the exposed portions more easily removed during the development operation S175. In other embodiments, during the development operation S175, the portions 50 in the resist layer exposed to radiation undergo a reaction that makes the exposed portions difficult to remove.

[0043] Next, in operation S160, the resist layer 15 undergoes a third heating or post-exposure baking (PEB). 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 300 seconds. In some embodiments, the post-exposure baking is performed at a temperature ranging from about 100° C. to about 230° C., while in other embodiments, the post-exposure baking is performed at a temperature ranging from about 150° C. to about 200° C. In some embodiments, the post-exposure baking operation S160 crosslinks the reaction product of the first compound or the first precursor with the second compound or the second precursor.

[0044] In some embodiments, Figure 5 As shown, after the post-exposure baking operation S160, the protective layer 20 is removed in operation S170. In some embodiments, the protective layer 20 prevents the degassing of the metal-containing resist layer 15. For example, during the post-exposure baking operation S160, smaller metal-containing compounds in the resist layer may become unstable during the post-exposure baking operation and degas from the resist layer 15. The metal-containing compounds may contaminate processing tools, semiconductor wafer processing tools or other semiconductor wafers being processed. The protective layer 20 prevents the metal-containing contaminants from degassing from the resist layer 15. In some embodiments, the protective layer 20 is removed by a suitable solvent.

[0045] The selectively exposed resist layer is then developed in operation S175. In some embodiments, the resist layer 15 is developed by applying a solvent-based developer 57 to the selectively exposed resist layer. Fig. 6A As shown, liquid developer 57 is supplied from dispenser 62 to resist 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 52 of the photoresist layer are removed by developer 57, forming a pattern of openings 55 in photoresist layer 15 to expose substrate 20, as shown in FIG. Figure 7 shown.

[0046] In some embodiments, the resist developer 57 includes a solvent and an acid or a base. In some embodiments, the concentration of the solvent is between about 60 wt.% and about 99 wt.% based on the total weight of the resist developer. The concentration of the acid or base is between about 0.001 wt.% and about 20 wt.% based on the total weight of the resist developer. In certain embodiments, the concentration of the acid or base in the developer is between about 0.01 wt.% and about 15 wt.% based on the total weight of the resist developer.

[0047] In some embodiments, the developer 57 is applied to the resist layer 15 using a spin coating process. In the spin coating process, the developer 57 is applied to the resist layer 15 from above the resist layer 15 while the resist coating substrate is being rotated, such as Fig. 6A As shown. In some embodiments, while the photoresist coated substrate 10 is rotated at a speed of about 100 rpm to about 2000 rpm, the developer 57 is supplied at a rate of about 5 ml / min to about 800 ml / min. In some embodiments, the developer is at a temperature between about 10° C. and about 80° C. In some embodiments, the developing operation lasts for about 30 seconds to about 10 minutes.

[0048] In some embodiments, the imaging agent 57 is an organic solvent. The organic solvent can be any suitable solvent. In some embodiments, the solvent is one or more selected from the following: propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl 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.

[0049] In some embodiments, before the developing operation S175, the protective layer 20 remains on the resist layer 15, and the protective layer 20 is removed during the developing operation S175. Figure 6B In some embodiments, the protective layer 20 is soluble in the developer 57 .

[0050] Although a spin coating operation is a suitable method for developing the photoresist layer 15 after exposure, it is intended to be illustrative rather than limiting of the embodiments. Instead, any suitable developing operation (including immersion processes, puddle processes, and spraying methods) may be used instead. All such developing operations are included within the scope of the embodiments.

[0051] In some embodiments, Figure 6C As shown, dry developer 105 is applied to the selectively exposed resist layer 15. In certain embodiments, dry developer 105 is plasma or chemical vapor, and dry development operation S180 is plasma etching or chemical etching operation. Dry development uses the difference related to composition, crosslinking degree and film density to selectively remove the required resist part. In certain embodiments, dry development process uses gentle plasma (high pressure, low power) or thermal process in a heated vacuum chamber when making dry development chemicals (such as BCl3, BF3 or other Lewis acids (lewis acid) in steam state) flow. In certain embodiments, BCl3 removes unexposed material, leaving the pattern of the exposed film transferred to the bottom layer by the etching process based on plasma.

[0052] 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 in a range of from about 5 mTorr to about 20 mTorr, at a power level in a range of from about 250 W to about 1000 W, at a temperature in a range of from 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.

[0053] After the development operation, additional processing is performed with the patterned photoresist layer 50 in place. For example, in some embodiments, an etching operation is performed using a dry or wet etch to transfer the pattern of the resist layer 50 to the underlying substrate 10, thereby forming a Figure 8 The recess 55' is shown. The substrate 10 has a different etch resistance than the resist layer 15. In some embodiments, the etchant is more selective to the substrate 10 than to the resist layer 15.

[0054] In some embodiments, during the etching operation in some embodiments, the exposed resist layer 15 is at least partially removed. In other embodiments, the exposed resist layer 15 is removed after etching the substrate 10 by selective etching, using a suitable resist stripper solvent, or by a resist plasma ashing operation.

[0055] In some embodiments, substrate 10 includes a single crystal semiconductor layer at least on a surface portion thereof. Substrate 10 may include a single crystal semiconductor material, such as but not limited to Si, Ge, SiGe, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs, GaSbP, GaAsSb, and InP. In some embodiments, substrate 10 is a silicon layer of a SOI (silicon on insulator) substrate. In some embodiments, substrate 10 is made of crystalline Si.

[0056] 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 crystal 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 an 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 % in the bottommost buffer layer to 70 atomic % in the topmost buffer layer.

[0057] In some embodiments, the substrate 10 includes at least one metal, metal alloy, and metal / nitride / sulfide / oxide / silicide (chemical formula: MX a ), wherein M is a metal, and X is N, S, Se, O, Si, and a is about 0.4 to about 2.5. In some embodiments, substrate 10 includes titanium, aluminum, cobalt, ruthenium, titanium nitride, tungsten nitride, tantalum nitride, and combinations thereof.

[0058] In some embodiments, the substrate 10 includes at least silicon or metal oxide or nitride (chemical 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, substrate 10 includes silicon dioxide, silicon nitride, aluminum oxide, hafnium oxide, lanthanum oxide, and combinations thereof.

[0059] The photoresist layer 15 is a photosensitive layer that is patterned by exposure to actinic radiation. Typically, the chemical properties of the photoresist areas affected by the incident radiation will change in a manner that depends on the type of photoresist used. The photoresist layer 15 is a positive tone resist or a negative tone resist. A positive tone resist refers to a photoresist material in which portions of the photoresist layer exposed to actinic radiation (e.g., UV light) are removed during development, while unexposed (or less exposed) photoresist areas remain on the substrate after the development operation. On the other hand, a negative tone resist refers to a photoresist material in which portions of the photoresist layer exposed to actinic radiation during development remain on the substrate after the development operation, while unexposed (or less exposed) photoresist areas are removed during the development operation.

[0060] In some embodiments, the photoresist layer 15 is made of a photoresist composition comprising a first compound or a first precursor and a second compound or a second precursor combined in a vapor state. The first precursor or the first compound is a first compound having a chemical formula M a R b X c Organic metals, such as Fig. 9A As shown, wherein M is at least one of the following: Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce or Lu; and R is a substituted or unsubstituted alkyl, alkenyl or carboxylic acid group. In some embodiments, M is selected from the group consisting of the following: Sn, Bi, Sb, In, Te and combinations thereof. In some embodiments, R is a C3-C6 alkyl, alkenyl or carboxylic acid group. In some embodiments, R is selected from the group consisting of the following: propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-penty, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, isohexyl, sec-hexyl, tert-hexyl and combinations thereof. X is a ligand, ion or other moiety that reacts with a second compound or a second precursor; and in some embodiments, 1≤a≤2, b≥1, c≥1 and b+c≤5. In some embodiments, the alkyl, alkenyl or carboxylic acid group is substituted with one or more fluorine groups. In some embodiments, the organometallic precursor is a dimer, such as Fig. 9A As shown, each monomer unit is connected by an amine group. Each monomer has the chemical formula: a R b X c , as described above.

[0061] 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 Cn F x H ((2n+1)-x) In some embodiments, R has at least one beta hydrogen or beta fluorine. In some embodiments, R is selected from the group consisting of isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, and sec-pentyl, and combinations thereof.

[0062] In some embodiments, X is any moiety that is easily replaced by a second compound or a second precursor to generate an M-OH moiety, such as a moiety selected from the group consisting of: an amine (including a dialkylamino group and a monoalkylamino group); an alkoxy group; a carboxylic acid group, a halogen, and a 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 includes a substituted or unsubstituted C1-C3 group.

[0063] In some embodiments, Fig. 9B As shown, the first organometallic compound or the first organometallic precursor includes a metal core M + , where the ligand L is attached to the metal core M + In some embodiments, the metal core M + It is a metal oxide. In certain embodiments, ligand L includes C3-C12 aliphatic or aromatic groups. The aliphatic or aromatic groups can be unbranched or branched (wherein containing 1-9 carbon (including alkyl groups, alkene groups and phenyl groups) cyclic or non-cyclic saturated side groups). The branched group can be further replaced with oxygen or halogen. In certain embodiments, C3-C12 aliphatic or aromatic groups include heterocyclic groups. In certain embodiments, C3-C12 aliphatic or aromatic groups are connected to metals by ether or ester bonds. In certain embodiments, C3-C12 aliphatic or aromatic groups include nitrite and sulfonate substituents.

[0064] 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), tert-amyltri(dimethylamino)tin, isopentyltri(dimethylamino)tin, n-amyltri(dimethylamino)tin, secondary butyltri(dimethylamino)tin, tert-butyltri(dimethylamino)tin, isobutyltri(dimethylamino)tin, n-butyltri(dimethylamino)tin, secondary propyltri(dimethylamino)tin, isopropyltri(dimethylamino)tin, n-propyltri(dimethylamino)tin, Propyl tri(diethylamino)tin and similar alkyl tri(tert-butoxy)tin compounds, including sec-hexyl tri(tert-butoxy)tin, tert-hexyl tri(tert-butoxy)tin, isohexyl tri(tert-butoxy)tin, n-hexyl tri(tert-butoxy)tin, sec-amyl tri(tert-butoxy), tert-amyl tri(tert-butoxy)tin, isopentyl tri(tert-butoxy)tin, n-amyl tri(tert-butoxy)tin, tert-butyl tri(tert-butoxy)tin, isobutyl tri(butoxy)tin, n-butyl tri(butoxy)tin, sec-butyl tri(butoxy)tin, isopropyl tri(dimethylamino)tin or n-propyl tri(butoxy)tin. In some embodiments, the organometallic precursor or organometallic compound is fluorinated. In some embodiments, the boiling point of the organometallic precursor or compound is less than about 200°C.

[0065] In some embodiments, the first compound or the first precursor includes one or more unsaturated bonds that can coordinate with functional groups (eg, hydroxyl groups) on the surface of the substrate or the intermediate underlying layer to improve the adhesion of the photoresist layer to the substrate or underlying layer.

[0066] In some embodiments, the second precursor or second compound is at least one of an amine, borane, phosphine, or water. In some embodiments, the amine has a chemical formula N p H n X m , wherein 0≤n≤3, 0≤m≤3, n+m=3 when p is 1, and n+m=4 when p is 2, and each X is independently a halogen selected from the group consisting of F, Cl, Br and I. In some embodiments, the borane has the chemical formula B p H n X m , wherein 0≤n≤3, 0≤m≤3, n+m=3 when p is 1, and n+m=4 when p is 2, and each X is independently a halogen selected from the group consisting of F, Cl, Br and I. In some embodiments, the phosphine has a chemical formula P p H n X m , wherein 0≤n≤3, 0≤m≤3, n+m=3 when p is 1, or n+m=4 when p is 2, and each X is independently a halogen selected from the group consisting of F, Cl, Br and I.

[0067] In some embodiments, the second precursor or compound is water, ammonia or hydrazine. The reaction product of water, ammonia or hydrazine and the organometallic precursor or compound can form hydrogen bonds, which can increase the boiling point of the reaction product and prevent the emission of the metal photoresist material, thereby preventing metal contamination. Hydrogen bonds can also help prevent the effect of moisture on the quality of the photoresist layer.

[0068] Fig. 9B The reaction that a metal precursor undergoes due to exposure to actinic radiation in some embodiments is shown. Due to exposure to actinic radiation, the ligand group L is removed from the metal core M of the metal precursor. + and two or more metal precursor cores are bonded to each other.

[0069] Fig. 9C An example of an organometallic precursor according to an embodiment of the present disclosure is shown. Fig. 9C In the above formula (A), Bz is a phenyl group.

[0070] 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).

[0071] exist Fig.10 2 shows a resist layer deposition apparatus 200 according to some embodiments of the present disclosure. In some embodiments, the deposition apparatus 200 is an ALD or CVD apparatus. The deposition apparatus 200 includes a vacuum chamber 205. A substrate support table 210 in the vacuum chamber 205 supports a substrate 10, such as a silicon wafer. In some embodiments, the substrate support table 210 includes a heater. In some embodiments, a first precursor or compound gas supply 220 and a carrier gas / purge gas supply 225 are connected to an inlet 230 in the chamber via a gas line 235, and a second precursor or compound gas supply 240 and a carrier gas / purge gas supply 225 are connected to another inlet 230' in the chamber via another gas line 235'. The chamber is evacuated, and excess reactants and reaction byproducts are removed by a vacuum pump 245 through an outlet 250 and an exhaust line 255. In some embodiments, the flow rates or pulses of precursor gases and carrier / purge gases, the exhaust of excess reactants and reaction byproducts, the pressure within the vacuum chamber 205, and the temperature of the vacuum chamber 205 or the wafer support table 210 are controlled by a controller 260 that is configured to control each of these parameters.

[0072] 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 205 (CVD chamber) via inlets 230, 230' 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 205 (ALD chamber) via inlets 230, 230' in an alternating manner, i.e., first one compound or a precursor, then the second compound or a precursor, and then the introduction of one compound or a precursor, then the second compound or a precursor is repeated alternately.

[0073] In some embodiments, the deposition chamber temperature is in the range of from about 30°C to about 400°C during the deposition operation, and in other embodiments is between about 50°C to about 250°C. In some embodiments, the pressure in the deposition chamber is in the range of from about 5mTorr to about 100Torr during the deposition operation, and in other embodiments is between about 100mTorr to about 10Torr. In some embodiments, the plasma power is less than about 1000W. In some embodiments, the plasma power ranges from 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 from 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 in the range of from about 1:1 to about 1:5. In some embodiments, under operating parameters outside the above-described ranges, unsatisfactory photoresist layers are produced. In some embodiments, photoresist layer formation occurs in a single chamber (one-step layer formation).

[0074] In the CVD process according to some embodiments of the present disclosure, two or more gas streams of an organic metal precursor and a second precursor (in separate inlet paths 230, 235 and 230', 235') are introduced into the deposition chamber 205 of the CVD device, where they mix and react in the gas phase to form a reaction product. In some embodiments, a separate injection inlet 230, 230' or a dual booster nozzle is used to introduce the gas flow. The deposition device is configured so that the gas flows of the organic metal precursor and the second precursor mix in the chamber, thereby allowing the organic metal precursor and the second precursor to react to form a reaction product. Without limiting the mechanism, function or use of the present disclosure, it is believed that the product from the gas phase reaction becomes heavier in molecular weight and is then condensed or otherwise deposited onto the substrate 10.

[0075] In some embodiments, the photoresist layer is deposited using an ALD process. During ALD, a layer is grown on substrate 10 by exposing the surface of the substrate to alternating gas compounds (or precursors). In contrast to CVD, the precursors are introduced as a series of continuous, non-overlapping pulses. In each of these pulses, the precursor molecules react with the surface in a self-limiting manner, so that the reaction terminates once all the reaction sites on the surface are consumed. Therefore, after a single exposure to all precursors (a so-called ALD cycle), the maximum amount of material deposited on the surface is determined by the nature of the precursor-surface interaction.

[0076] In an embodiment of the ALD process, in the first half of the reaction, an organometallic precursor is delivered in a pulsed form to deliver a metal-containing precursor to the surface of the substrate 10. In some embodiments, the organometallic precursor reacts with a suitable underlying species (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 evacuating with a vacuum pump 245 and / or by flowing an inert purge gas. Then, in some embodiments, a second precursor (e.g., ammonia (NH3)) is delivered to the deposition chamber in a pulsed form. NH3 reacts with the organometallic precursor on the substrate to obtain a reaction product photoresist on the substrate surface. The second precursor also forms a self-saturated bond with the underlying reactive species 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 delivery of the first and second precursors in a pulsed form is alternated with the intermediate purge operation until the desired thickness of the photoresist layer is reached.

[0077] In some embodiments, the photoresist layer 15 is formed to a thickness of about 5 nm to about 50 nm, and in other embodiments is formed to a thickness of about 10 nm to about 30 nm. Those of ordinary skill in the art will recognize that additional thickness ranges within the above-defined ranges are expected and within the scope of the present disclosure. Based on the optical properties of the photoresist layer, non-contact x-ray reflectivity methods and / or ellipsometry can be used to evaluate the thickness. In some embodiments, the thickness of each photoresist layer is relatively uniform for processing. In some embodiments, the thickness variation of the deposited photoresist layer does not exceed ±25% compared to the average thickness, and in other embodiments, the thickness of each photoresist layer does not exceed ±10% compared to the average photoresist layer thickness. In some embodiments, such as high uniformity deposition on a larger substrate, the evaluation of the uniformity of the photoresist layer can be evaluated using a 1 cm edge exclusion, that is, for the portion of the coating within 1 cm of the edge, the layer uniformity is not evaluated. Those of ordinary skill in the art will recognize that additional ranges within the above-defined ranges are expected and within the scope of the present disclosure.

[0078] In some embodiments, a carrier gas is used to deliver the first and second compounds or precursors into the deposition chamber 205. The carrier gas, purge gas, deposition gas, or other process gas may contain nitrogen, hydrogen, argon, neon, helium, or combinations thereof.

[0079] In some embodiments, the organometallic compound includes tin (Sn), antimony (Sb), bismuth (Bi), indium (In), and / or tellurium (Te) as metal components, however, the present disclosure is not limited to these metals. In other embodiments, additional suitable metals include titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), cobalt (Co), molybdenum (Mo), tungsten (W), aluminum (Al), gallium (Ga), silicon (Si), germanium (Ge), phosphorus (P), arsenic (As), yttrium (Y), lanthanum (La), cerium (Ce), lutetium (Lu), or a combination thereof. The additional metal may be a substitute or supplement for Sn, Sb, Bi, In, and / or Te.

[0080] The specific metal used may significantly affect the absorption of radiation. Therefore, the metal component can be selected based on the desired radiation and absorption cross section. Tin, antimony, bismuth, tellurium and indium provide strong absorption of extreme ultraviolet radiation at 13.5nm. Hafnium provides good absorption of electron beams and extreme ultraviolet radiation. Metal compositions including titanium, vanadium, molybdenum or tungsten have strong absorption at longer wavelengths to provide sensitivity to ultraviolet radiation at, for example, a wavelength of 248nm.

[0081] Fig.11 The reactions that components of photoresist compositions according to embodiments of the present disclosure undergo as a result of exposure to actinic radiation and heat are shown. Fig.11 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.11 As shown, the photoresist composition includes an organic metal compound, such as S n X2R2 and a second compound, such as ammonia (NH3). When the organometallic compound is combined with ammonia, the organometallic compound and some of the ammonia react in the gas phase to form a reaction product having an amine group of a metal (Sn) attached to the organometallic compound. The amine groups in the deposited photoresist layer have hydrogen bonds, which can significantly increase the boiling point of the deposited photoresist layer and prevent the metal-containing photoresist material from outgassing, thereby preventing the metal in the metal-containing photoresist from contaminating the deposition chamber and semiconductor device processing equipment. In addition, the hydrogen bonds of the amine groups can control the effect of moisture on the quality of the photoresist layer.

[0082] When subsequently exposed to EUV radiation, the organometallic compound absorbs the EUV radiation and one or more organic R groups are cleaved from the organometallic compound to form an aminometallic compound in the radiation exposed areas. Then, in some embodiments, when a post-exposure bake (PEB) is performed, the aminometallic compound is cross-linked through the amine groups, such as Fig.11 In some embodiments, partial crosslinking of the amide metal compound occurs as a result of exposure to extreme ultraviolet radiation.

[0083] In some embodiments, protective layer 20 includes polymer. In some embodiments, polymer is at least one of the following: polyvinyl alcohol, polyacrylic acid, polymethyl methacrylate, polyacrylamide, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyhydroxystyrene or polymethacrylic acid. In some embodiments, polymer has a molecular weight in the range of from about 1000 dalton to about 10000 dalton. In some embodiments, polymer has a molecular weight in the range of from about 2000 dalton to about 8000 dalton. Polymers with molecular weight less than about 1000 dalton may not be able to fully suppress metal-containing resist exhaust. Polymers with molecular weight greater than about 10000 dalton may be difficult to completely remove subsequently, and cause the resist pattern resolution to decrease. In some embodiments, the thickness of protective layer 20 is in the range of from about 3nm to about 100nm. In some embodiments, the thickness of protective layer is in the range of from about 15nm to about 80nm. When the thickness is less than 3nm, protective layer cannot fully suppress metal-containing resist exhaust. When the thickness is greater than about 100 nm, it may be difficult to subsequently completely remove the protective layer, resulting in reduced resolution of the resist pattern.

[0084] In some embodiments, forming the protective layer 20 includes: combining a polymer and a solvent to form a protective layer composition, depositing the protective layer composition on the resist layer 15, and removing the solvent from the protective layer composition. In some embodiments, depositing the protective layer composition includes spin coating the protective layer composition on the resist layer 15. In some embodiments, removing the solvent from the protective layer composition includes heating the protective layer 20 at a temperature in a range from about 40° C. to about 150° C. for about 10 seconds to about 10 minutes.

[0085] In some embodiments, the solvent is at least one of ethers, including propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), ethyl ether, diisoamyl ether (DIAE) and 1-ethoxy-2-propanol (PGEE); γ-butyrolactone (GBL); cyclohexanone (CHN); ethyl lactate (EL); alcohols, including methanol, ethanol, propanol, isopropanol (IPA), n-butanol, 4-methyl-2-pentanol; ketones, including acetone, methyl ethyl ketone and 2-heptanone (MAK); dimethylformamide (DMF); tetrahydrofuran (THF); methyl isobutyl carbinol (MIBC); n-butyl acetate (nBA); tetrahydrofuran (THF); 1,4-dioxane; alkanes; and deionized water. In some embodiments, the polymer is soluble in the solvent, and the underlying resist layer is insoluble in the solvent.

[0086] In some embodiments, protective layer 20 is not a photoresist layer. In some embodiments, the portion of protective layer 20 that is selectively exposed to actinic radiation does not undergo a crosslinking reaction. In some embodiments, the composition of the protective layer is not photosensitive to the actinic radiation used to selectively expose resist layer 15. In some embodiments, protective layer 20 does not affect the actinic radiation absorption of resist layer 15.

[0087] In some embodiments, the solvent is a polar solvent, including at least one of deionized water, alcohol or ketone. In some embodiments, the polar solvent includes at least one of IPA, PGME, DMSO or water. In some embodiments, the protective layer 20 composition includes a polar solvent and the polymer is a hydrophilic polymer. In some embodiments, the hydrophilic polymer is at least one of polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyacrylamide or polyhydroxystyrene. Their hydrophilic polymers provide a protective layer with a hydrophilic top surface. The hydrophilic polymer can improve the solubility in the solvent for removing the protective layer, and can improve the resolution of the resist layer. In some embodiments, the hydrophilic polymer protective layer improves the development operation of the resist layer 15, thereby improving the pattern resolution.

[0088] In some embodiments, the solvent is a non-polar solvent, including at least one of the following: ether (e.g., diethyl ether or DIAE); alkane; or 1,4-dioxane, and the polymer is a hydrophobic polymer. In some embodiments, the hydrophobic polymer is at least one of polytetrafluoroethylene, polyethylene, polypropylene, or polystyrene. In some embodiments, the hydrophobic polymer provides a hydrophobic surface that prevents moisture in the environment from entering the resist layer and reduces the performance of the resist layer. The resist layer 15 absorbs moisture and may cause the resist layer 15 to be excessively cross-linked, including in the unexposed portion of the resist layer that may not need to be cross-linked. Therefore, in some embodiments, the hydrophobic surface improves pattern resolution.

[0089] The protective layer 20 is removed by any solvent disclosed herein. In other embodiments, the protective layer is removed by ultraviolet radiation, heat treatment, etching, or resist developer.

[0090] In some embodiments, Fig.12 As shown, before forming the photoresist layer, a layer to be patterned (target layer) 60 is disposed on the substrate. In some embodiments, the layer to be patterned 60 is a metallization layer or a dielectric layer disposed on the metallization layer, such as a passivation layer. In embodiments where the layer to be patterned 60 is a metallization layer, the layer to be patterned 60 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 to be patterned 60 is a dielectric layer, the layer to be patterned 60 is formed by a dielectric layer formation technique (including thermal oxidation, chemical vapor deposition, atomic layer deposition, and physical vapor deposition).

[0091] In some embodiments, the resist layer 15 is then subjected to an optional first heating operation at a temperature between about 40° C. and about 150° C. for about 10 seconds to about 10 minutes. After the optional first heating operation or the formation of the resist layer, a protective layer 20 is formed on the resist layer 15, such as Fig.13 As shown. The protective layer 20 and the reference Figure 3 The protective layer described is the same. In some embodiments, the protective layer 20 is then heated in a second heating operation to remove the solvent or dry the protective layer at a temperature between about 40° C. and about 150° C. for about 10 seconds to about 10 minutes.

[0092] The photoresist layer 15 and the protective layer 20 are then selectively exposed to actinic radiation 45 to form exposed areas 50 and unexposed areas 52 in the photoresist layer, as shown in FIG. Fig.14A and 14B As shown in this article, Figure 4A and 4B As described herein, in some embodiments, the photoresist is a negative tone photoresist.

[0093] Next, the resist layer 15 and the protective layer 20 are subjected to a third heating or post-exposure baking (PEB). In some embodiments, the resist layer 15 and the protective layer 20 are heated to a temperature of about 50° C. to about 250° C. for about 20 seconds to about 300 seconds. In some embodiments, the post-exposure baking is performed at a temperature in a range from about 100° C. to about 230° C., and in other embodiments, at a temperature in a range from about 150° C. to about 200° C.

[0094] In some embodiments, Fig.15 As shown, the protective layer 20 is subsequently removed after a post-exposure bake operation.

[0095] like Fig.16A As shown, the unexposed photoresist area 52 is developed by dispensing developer 57 from dispenser 62. In some embodiments, as Fig. 16B As shown, the protective layer 20 is removed during the development operation. In other embodiments, the unexposed photoresist areas are developed by a dry development operation, such as Fig. 16C The development operation forms a photoresist pattern 55, as shown. Fig.17 The development operation is similar to that of this article. Fig. 6A , Figure 6B , Figure 6C and Figure 7 The operation explained is similar.

[0096] Then, if Fig.18 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 reference Figure 8 As explained, to form a pattern 55" in the layer 60 to be patterned.

[0097] 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. These embodiments also include etching the substrate through openings of a 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; and epitaxially growing or recessing STI features to form fin-shaped active areas. 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 can be manufactured and / or improved using the methods described herein.

[0098] 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, other memory cells, and combinations thereof are formed according to embodiments of the present disclosure.

[0099] Embodiments of the present disclosure provide uniform photoresist films deposited on the surface of a semiconductor substrate. In some embodiments, metals in metal-containing photoresists are prevented from contaminating deposition chambers and semiconductor substrate processing equipment. Photoresist moisture sensitivity issues are prevented by methods according to embodiments of the present disclosure. Embodiments of the present disclosure provide improved pattern resolution. Embodiments of the present disclosure provide improved line width roughness.

[0100] One embodiment of the present disclosure is a method for manufacturing a semiconductor device, comprising: forming a photoresist layer on a substrate, comprising: combining a first precursor and a second precursor in a vapor state to form a photoresist material, and depositing the photoresist material on the substrate. A protective layer is formed on the photoresist layer. The photoresist layer is selectively exposed to actinic radiation through the protective layer to form a latent pattern in the photoresist layer. The protective layer is removed, and the latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern. In an embodiment, the protective layer includes a hydrophilic polymer. In an embodiment, the protective layer includes a hydrophobic polymer. In an embodiment, the protective layer includes a polymer selected from the group consisting of: polyvinyl alcohol, polyacrylic acid, polymethyl methacrylate, polyacrylamide, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyhydroxystyrene, polymethacrylic acid, and combinations thereof. In an embodiment, the protective layer includes a polymer. In an embodiment, the polymer has a molecular weight in the range of from 1000 Daltons to 10000 Daltons. In an embodiment, forming the protective layer over the photoresist layer comprises spin coating a mixture of a polymer and a solvent over the substrate. In an embodiment, the first precursor is an organometallic having the following chemical formula: a R b X c, wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, or Lu; R is a substituted or unsubstituted alkyl, alkenyl, or carboxylic acid group; X is a halide or sulfonate group; and 1≤a≤2, b≥1, c≥1, and b+c≤5; and the second precursor is at least one of an amine, borane, phosphine, or water. In an embodiment, the method includes heating the photoresist layer after selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before removing the protective layer. In an embodiment, the method includes heating the photoresist layer after forming a protective layer over the photoresist layer and before selectively exposing the photoresist layer to actinic radiation. In an embodiment, the protective layer is removed during development of the latent pattern. In an embodiment, the photoresist material is deposited over the substrate by atomic layer deposition (ALD) or chemical vapor deposition (CVD).

[0101] Another embodiment of the present disclosure is a method of manufacturing a semiconductor device, comprising depositing a photoresist composition on a substrate surface via atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form a photoresist layer, the photoresist composition comprising a first organometallic compound and a second compound. A protective layer comprising a polymer is formed on the photoresist layer. The photoresist layer is selectively exposed to actinic radiation through the protective layer to form a latent pattern. The protective layer is removed, and the latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern that exposes a portion of the substrate surface. The portion of the substrate surface exposed by the development is removed. In an embodiment, the first organometallic compound is at least one of the following: secondary hexyltri(dimethylamino)tin, tert-hexyltri(dimethylamino)tin, isohexyltri(dimethylamino)tin, n-hexyltri(dimethylamino)tin, secondary amyltri(dimethylamino), tert-amyltri(dimethylamino)tin, isopentyltri(dimethylamino)tin, n-amyltri(dimethylamino)tin, secondary butyltri(dimethylamino)tin, tert-butyltri(dimethylamino)tin, isobutyltri(dimethylamino)tin, n-butyltri(dimethylamino)tin, secondary propyltri(dimethylamino)tin, isopropyltri(dimethylamino)tin, n-propyltri(diethylamino)tin, and Similar alkyl tri(tert-butoxy)tin compounds include sec-hexyl tri(tert-butoxy)tin, tert-hexyl tri(tert-butoxy)tin, isohexyl tri(tert-butoxy)tin, n-hexyl tri(tert-butoxy)tin, sec-amyl tri(tert-butoxy), tert-amyl tri(tert-butoxy)tin, isoamyl tri(tert-butoxy)tin, n-amyl tri(tert-butoxy)tin, tert-butyl tri(tert-butoxy)tin, isobutyl tri(butoxy)tin, n-butyl tri(butoxy)tin, sec-butyl tri(butoxy)tin, isopropyl tri(dimethylamino)tin or n-propyl tri(butoxy)tin; and the second compound is at least one of an amine, borane, phosphine or water. In an embodiment, removing a portion of the substrate surface by developing includes etching the substrate surface. In an 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 through the protective layer to form a latent pattern and before removing the protective layer. In an embodiment, the polymer is at least one of a hydrophilic polymer or a hydrophobic polymer. In an embodiment, the polymer is at least one of polyvinyl alcohol, polyacrylic acid, polymethyl methacrylate, polyacrylamide, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyhydroxystyrene, or polymethacrylic acid. In an embodiment, the developer is a dry developer. In an embodiment, the method includes heating the protective layer and the photoresist layer at a temperature in the range of 40° C. to 150° C. after forming a protective layer on the photoresist layer and before selectively exposing the photoresist layer to actinic radiation through the protective layer.In an embodiment, the protective layer comprises: mixing a polymer and a solvent to form a protective layer composition, spin coating the protective layer composition on the photoresist layer, and removing the solvent from the protective layer composition. In an embodiment, the actinic radiation is extreme ultraviolet radiation. In an embodiment, the method comprises heating the photoresist layer before forming the protective layer.

[0102] Another embodiment of the present disclosure is a method for manufacturing a semiconductor device, comprising: 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 via chemical vapor deposition (CVD) to form a layer of the composition of the first compound and the second compound. The first compound is an organometallic compound, and the second compound is at least one of an amine, borane, phosphine, or water. A protective layer is formed by coating a protective layer composition on the layer of the composition of the first compound and the second compound, the protective layer composition comprising a polymer and a solvent. The layer of the composition of the first compound and the second compound is exposed to actinic radiation in a pattern through the protective layer to form a latent pattern in the layer of the composition of the first compound and the second compound. Removing the protective layer; and developing the layer of the composition exposed in a pattern to form a patterned layer of the composition of the first compound and the second compound. In an embodiment, the protective layer composition is not photosensitized to actinic radiation. In an embodiment, after selectively exposing the layer of the composition of the first compound and the second compound to actinic radiation through the protective layer to form a latent pattern and before removing the protective layer, the layer of the composition of the first compound and the second compound is heated at a temperature in the range of from 100°C to 200°C. In an embodiment, the solvent is a polar solvent and the polymer is a hydrophilic polymer. In an embodiment, the solvent is a non-polar solvent and the polymer is a hydrophobic polymer. In an embodiment, the solvent is a polar solvent and the polymer is at least one of polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyacrylamide, or polyhydroxystyrene. In an embodiment, the solvent is a non-polar solvent and the polymer is at least one of polytetrafluoroethylene, polyethylene, polypropylene, or polystyrene. In an embodiment, the actinic radiation is extreme ultraviolet radiation. In an embodiment, the method includes heating the layer of the composition of the first compound and the second compound before forming the protective layer. In an embodiment, the method includes removing a portion of the substrate exposed by development. In an embodiment, removing a portion of the substrate by development includes etching the substrate. In an embodiment, the development is a dry development operation.

[0103] Another embodiment of the present disclosure is a method for patterning a resist layer, comprising: depositing a resist layer on a substrate surface by atomic layer deposition (ALD) or chemical vapor deposition (CVD). The resist layer includes a reaction product of an organic metal compound and at least one of an amine, borane, phosphine, and water. A protective layer is formed on the resist layer. After forming the protective layer, the resist layer is cross-linked in a pattern to form a latent pattern in the resist layer. The protective layer is removed, and the latent pattern is developed by applying a developer to the resist layer cross-linked in a pattern to form a pattern that exposes a portion of the substrate surface. In an embodiment, the method includes removing the exposed portion of the substrate surface after development. In an embodiment, the organic metal compound includes a metal selected from the group consisting of Sn, Bi, Sb, In, and Te. In an embodiment, the protective layer is not cross-linked during the cross-linking of the resist layer in a pattern. In an embodiment, forming the protective layer includes: combining a polymer and a solvent to form a protective layer composition, spin-coating the protective layer composition on the resist layer, and removing the solvent from the protective layer composition. In an embodiment, the solvent is a polar solvent and the polymer is at least one of polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyacrylamide, or polyhydroxystyrene. In an embodiment, the solvent is a non-polar solvent and the polymer is at least one of polytetrafluoroethylene, polyethylene, polypropylene, or polystyrene. In an embodiment, the amine, borane, or phosphine comprises a halide substituent. In an embodiment, pattern-crosslinking the resist layer comprises exposing the resist layer to extreme ultraviolet radiation in a pattern, and heating the pattern-exposed resist layer and the protective layer. In an embodiment, the pattern-exposed resist layer is heated at a temperature in a range from 100° C. to 200° C.

[0104] 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 over the substrate surface. The organometallic compound has a chemical formula: M a R b X c, wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, or Lu; R is a substituted or unsubstituted alkyl, alkenyl, or carboxylic acid group; X is a halide or sulfonate group; and 1≤a≤2, b≥1, c≥1, and b+c≤5. The second gas phase compound is at least one of an amine, a borane, a phosphine, or water. A protective layer is formed over the resist layer. The resist layer is pattern-crosslinked to form a latent pattern in the resist layer. After the resist layer is pattern-crosslinked, the protective layer is removed, and the latent pattern is developed by applying a developer to the resist layer crosslinked in the pattern to form a pattern exposing a portion of the substrate surface. In an embodiment, the amine, borane, or phosphine includes a halide substitute. In an embodiment, the protective layer is removed during the development of the latent pattern. In an embodiment, pattern-crosslinking the resist layer comprises exposing the resist layer to extreme ultraviolet radiation in a pattern through the protective layer, and heating the pattern-exposed resist layer. In an embodiment, the pattern-exposed resist layer is heated at a temperature in the range of 100° C. to 200° C. In an embodiment, the method comprises removing a portion of the substrate exposed by development. In an embodiment, the method comprises heating the resist layer at a temperature in the range of 40° C. to 150° C. before pattern-crosslinking the resist layer. In an embodiment, forming a protective layer comprises: combining a polymer and a solvent to form a protective layer composition, depositing the protective layer composition on the resist layer, and removing the solvent from the protective layer composition. In an embodiment, the solvent is a polar solvent and the polymer is at least one of polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyacrylamide, or polyhydroxystyrene. In an embodiment, the solvent is a non-polar solvent and the polymer is at least one of polytetrafluoroethylene, polyethylene, polypropylene, or polystyrene.

[0105] Another embodiment of the present invention is a method for patterning a photoresist layer, comprising depositing a photoresist layer on a substrate by a vapor deposition operation. The photoresist layer comprises a reaction product of an organic metal compound and a second compound, wherein the second compound is at least one of an amine, borane, phosphine or water. A protective layer composition comprising a polymer and a solvent is applied to the photoresist layer to form a protective layer. The photoresist layer is selectively exposed to actinic radiation through the protective layer to form a latent pattern in the photoresist layer. The protective layer is removed, and portions of the photoresist layer that are not exposed to actinic radiation are removed to form a pattern of the remaining portions of the photoresist layer that are exposed to actinic radiation during the selective exposure of the photoresist layer. In an embodiment, the method comprises removing portions of the substrate exposed by the removed portion of the photoresist layer. In an embodiment, removing portions of the substrate comprises dry etching the substrate. In an embodiment, removing portions of the photoresist layer comprises applying plasma to the photoresist layer. In an embodiment, the vapor deposition operation comprises atomic layer deposition or chemical vapor deposition. In an embodiment, the protective layer is not photosensitive to actinic radiation. In an embodiment, the method comprises heating the protective layer and 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 an embodiment, the protective layer is removed during the removal of the portion of the photoresist layer not exposed to actinic radiation. In an embodiment, the method comprises heating the protective layer and the photoresist layer at a temperature in the range of 40° C. to 150° C. before selectively exposing the photoresist layer to actinic radiation. In an embodiment, the amine is ammonia or hydrazine.

[0106] 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 achieve the same purpose and / or achieve the same advantages of the embodiments or examples introduced herein. Those skilled in the art should also recognize that such equivalent structures do not deviate from the spirit and scope of the present disclosure, and they can make various changes, substitutions and modifications in the present disclosure without departing from the spirit and scope of the present disclosure.

[0107] Example 1 is a method for 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, and depositing the photoresist material over the substrate; forming a protective layer over the photoresist layer; selectively exposing the photoresist layer to actinic radiation through the protective layer to form a latent pattern in the photoresist layer; removing the protective layer; and developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern.

[0108] Example 2 is the method of Example 1, wherein the protective layer includes a hydrophilic polymer.

[0109] Example 3 is the method of Example 1, wherein the protective layer includes a hydrophobic polymer.

[0110] Example 4 is the method of Example 1, wherein the protective layer includes a polymer selected from the group consisting of polyvinyl alcohol, polyacrylic acid, polymethyl methacrylate, polyacrylamide, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyhydroxystyrene, polymethacrylic acid, and combinations thereof.

[0111] Example 5 is the method of Example 1, wherein forming a protective layer over the photoresist layer comprises spin coating a mixture of a polymer and a solvent over the substrate.

[0112] Example 6 is the method of Example 1, wherein the first precursor is an organometallic having the following chemical formula: a R b X c , wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, or Lu, R is a substituted or unsubstituted alkyl, alkenyl, or carboxylic acid group, X is a halide or sulfonate group, and 1≤a≤2, b≥1, c≥1, and b+c≤5; and the second precursor is at least one of an amine, borane, phosphine, or water.

[0113] Example 7 is the method of Example 1, further comprising: heating the photoresist layer after selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before removing the protective layer.

[0114] Example 8 is the method of Example 1, further comprising heating the photoresist layer after forming the protective layer over the photoresist layer and before selectively exposing the photoresist layer to actinic radiation.

[0115] Example 9 is the method of Example 1, wherein the protective layer is removed during developing the latent pattern.

[0116] Example 10 is the method of Example 1, wherein the photoresist material is deposited on the substrate by atomic layer deposition (ALD) or chemical vapor deposition (CVD).

[0117] Example 11 is a method for manufacturing a semiconductor device, comprising: depositing a photoresist composition on a substrate surface via atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form a photoresist layer, the photoresist composition comprising a first organic metal compound and a second compound; forming a protective layer comprising a polymer on the photoresist layer; selectively exposing the photoresist layer to actinic radiation through the protective layer to form a latent pattern; removing the protective layer; developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern exposing a portion of the substrate surface; and removing the portion of the substrate surface exposed by the development.

[0118] Example 12 is the method described in Example 11, wherein the first organometallic 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), 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 propyl 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-pentyltri(tert-butoxy), tert-pentyltri(tert-butoxy)tin, isopentyltri(tert-butoxy)tin, n-pentyltri(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, borane, phosphine or water.

[0119] Example 13 is the method of Example 11, wherein removing a portion of the substrate surface by the developing includes etching the substrate surface.

[0120] Example 14 is the method described in Example 11, further comprising: heating the photoresist layer at a temperature in a range from 100°C to 200°C after selectively exposing the photoresist layer to actinic radiation through the protective layer to form a latent pattern, and before removing the protective layer.

[0121] Example 15 is the method of Example 11, wherein the polymer is at least one of a hydrophilic polymer or a hydrophobic polymer.

[0122] Example 16 is a method for manufacturing a semiconductor device, comprising: simultaneously introducing a first compound and a second compound into a 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 via chemical vapor deposition (CVD) to form a layer of the composition of the first compound and the second compound, wherein the first compound is an organic metal compound and the second compound is at least one of an amine, borane, phosphine or water; forming a protective layer by coating a protective layer composition on the layer of the composition of the first compound and the second compound, the protective layer composition comprising a polymer and a solvent; exposing the layer of the composition of the first compound and the second compound to actinic radiation in a pattern through the protective layer to form a latent pattern in the layer of the composition of the first compound and the second compound; removing the protective layer; and developing the layer of the composition exposed in the pattern to form a patterned layer of the composition of the first compound and the second compound.

[0123] Example 17 is the method of Example 16, wherein the protective layer composition is not photosensitized to the actinic radiation.

[0124] Example 18 is the method described in Example 16, further comprising: heating the layer of the composition of the first compound and the second compound at a temperature in a range from 100°C to 200°C after selectively exposing the layer of the composition of the first compound and the second compound to actinic radiation through the protective layer to form a latent pattern and before removing the protective layer.

[0125] Example 19 is the method of Example 16, wherein the solvent is a polar solvent and the polymer is a hydrophilic polymer.

[0126] Example 20 is the method of Example 16, wherein the solvent is a non-polar solvent and the polymer is a hydrophobic polymer.

Claims

1. A method for manufacturing a semiconductor device, comprising: A photoresist layer is formed on the substrate, comprising: combining the first precursor and the second precursor in a vapor state to form a photoresist material, and depositing the photoresist material over the substrate; forming a protective layer on the photoresist layer; selectively exposing the photoresist layer to actinic radiation through the protective layer to form a latent pattern in the photoresist layer; removing the protective layer; and developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern, Wherein, the first precursor is an organic metal having the following chemical formula: M a R b X c wherein M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce or Lu, R is a substituted or unsubstituted alkyl, alkenyl or carboxylic acid group, X is a halide or sulfonate group, and 1≤a≤2, b≥1, c≥1, and b+c≤5; and The second precursor is at least one of amine, borane, phosphine or water.

2. The method according to claim 1, wherein: The protective layer includes a hydrophilic polymer.

3. The method according to claim 1, wherein: The protective layer includes a hydrophobic polymer.

4. The method according to claim 1, wherein: The protective layer includes a polymer selected from the group consisting of polyvinyl alcohol, polyacrylic acid, polymethyl methacrylate, polyacrylamide, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyhydroxystyrene, polymethacrylic acid, and combinations thereof.

5. The method according to claim 1, wherein: Forming a protective layer over the photoresist layer includes spin coating a mixture of a polymer and a solvent over the substrate.

6. The method according to claim 1, further comprising: After selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before removing the protective layer, the photoresist layer is heated.

7. The method according to claim 1, further comprising: The photoresist layer is heated after forming the protective layer over the photoresist layer and before selectively exposing the photoresist layer to actinic radiation.

8. The method according to claim 1, wherein: The protective layer is removed during development of the latent pattern.

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

10. A method for manufacturing a semiconductor device, comprising: depositing a photoresist composition over a surface of a substrate via atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form a photoresist layer, the photoresist composition comprising a first organometallic compound and a second compound; forming a protective layer including a polymer over the photoresist layer; selectively exposing the photoresist layer to actinic radiation through the protective layer to form a latent pattern; removing the protective layer; developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern exposing a portion of the substrate surface; as well as removing a portion of the substrate surface exposed by the developing, The method 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 through the protective layer to form a latent pattern and before removing the protective layer.

11. The method according to claim 10, wherein: The first organometallic compound is at least one of the following: secondary hexyltri(dimethylamino)tin, tert-hexyltri(dimethylamino)tin, isohexyltri(dimethylamino)tin, n-hexyltri(dimethylamino)tin, secondary amyltri(dimethylamino), tert-amyltri(dimethylamino)tin, isopentyltri(dimethylamino)tin, n-amyltri(dimethylamino)tin, secondary butyltri(dimethylamino)tin, tert-butyltri(dimethylamino)tin, isobutyltri(dimethylamino)tin, n-butyltri(dimethylamino)tin, secondary propyltri(dimethylamino)tin, isopropyltri(dimethylamino)tin, n-propyltri(dimethylamino)tin tri(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), 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 amine, borane, phosphine or water.

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

13. The method according to claim 10, wherein: The polymer is at least one of a hydrophilic polymer or a hydrophobic polymer.

14. A method for manufacturing a semiconductor device, comprising: simultaneously introducing a first compound and a second compound into a chamber to form a combination of the first compound and the second compound; depositing the combination of the first compound and the second compound on a substrate via chemical vapor deposition (CVD) to form a layer of the combination of the first compound and the second compound, wherein the first compound is an organometallic compound, and the second compound is at least one of an amine, borane, phosphine or water; forming a protective layer by coating a protective layer composition on the layer of the composition of the first compound and the second compound, the protective layer composition comprising a polymer and a solvent; pattern-wise exposing the layer of the combination of the first compound and the second compound to actinic radiation through the protective layer to form a latent pattern in the layer of the combination of the first compound and the second compound; removing the protective layer; and developing the patternwise exposed layer of the composition to form a patterned layer of the composition of the first compound and the second compound, The method further includes: heating the layer of the composition of the first compound and the second compound at a temperature ranging from 100°C to 200°C after selectively exposing the layer of the composition of the first compound and the second compound to actinic radiation through the protective layer to form a latent pattern and before removing the protective layer.

15. The method according to claim 14, wherein: The protective layer composition is insensitive to the actinic radiation.

16. The method according to claim 14, wherein: The solvent is a polar solvent and the polymer is a hydrophilic polymer.

17. The method according to claim 14, wherein: The solvent is a non-polar solvent and the polymer is a hydrophobic polymer.

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