Method of manufacturing a semiconductor device

Abstract

A method of manufacturing a semiconductor device includes forming a photoresist structure, including forming a photoresist layer including a photoresist composition on a substrate. After forming the photoresist layer, the photoresist layer is treated with an additive. The additive is selected from one or more of the group consisting of a radical inhibitor, a thermal radical inhibitor, and a photo radical inhibitor.

Description

Technical Field

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

[0002] As consumer devices become smaller to meet consumer demands, the individual components of the devices also need to be downsized. Semiconductor devices are a major component of devices such as mobile phones and computer tablets and are under increasing pressure to become smaller, and individual devices within the semiconductor device (such as transistors, resistors, and capacitors, etc.) are also under corresponding pressure to be downsized.

[0003] One enabling technology used in semiconductor device manufacturing is the use of lithography materials. Such materials are applied to the surface of the layer to be patterned and are exposed to energy for patterning. Such exposure changes the chemical and physical properties of the photosensitive material in the exposed area. This change, combined with the unchanged photosensitive material in the non-exposed area, can be used to remove one area without removing the other.

[0004] However, as the size of individual devices shrinks, the range that lithography can handle also becomes narrower. Therefore, it is necessary to make progress in the field of lithography processing to maintain the ability to downsize devices, and further improvements are also necessary to meet the required design standards and thus continue to move towards smaller and smaller components. Summary of the Invention

[0005] The present disclosure relates to a method of manufacturing a semiconductor device. In some embodiments, the method includes forming a photoresist structure, including forming a photoresist layer including a photoresist composition on a substrate; and after forming the photoresist layer, treating the photoresist layer with an additive, where the additive is one or more selected from the group consisting of free radical inhibitors, thermal free radical inhibitors, and photo free radical inhibitors.

[0006] In some embodiments, the method includes forming a metal-containing photoresist layer on a substrate; forming a first layer on the substrate before forming the metal-containing photoresist layer, or forming a first layer on the metal-containing photoresist layer after forming the metal-containing photoresist layer; and diffusing the additive from the first layer into the metal-containing photoresist layer, where the additive is one or more selected from the group consisting of free radical inhibitors, thermal free radical inhibitors, and photo free radical inhibitors.

[0007] In some embodiments, the method includes forming a photoresist layer on a substrate, where the photoresist layer includes a metal photoresist composition; forming a top layer on the photoresist layer, where the top layer includes a polymer and a radical-inhibiting compound; patternwise exposing the photoresist layer to actinic radiation; and developing the patternwise exposed photoresist layer to form a pattern in the photoresist layer. Brief Description of the Drawings

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

[0009] Figure 1 The manufacturing process flow of a semiconductor device is described according to the disclosed embodiments;

[0010] Figure 2 The manufacturing process flow of a semiconductor device is described according to the disclosed embodiments;

[0011] Figure 3 The manufacturing process flow of a semiconductor device is described according to the disclosed embodiments;

[0012] Figure 4 The manufacturing process flow of a semiconductor device is described according to the disclosed embodiments;

[0013] Figure 5 The manufacturing process flow of a semiconductor device is described according to the disclosed embodiments;

[0014] Figure 6A 、 Figure 6B 、 Figure 6C and Figure 6D The process stages are described in order according to the disclosed embodiments;

[0015] Figure 7A 、 Figure 7B and Figure 7C Describing sequential process stages of an operation according to disclosed embodiments;

[0016] Figure 8A 、 Figure 8B 、 Figure 8C 、 Figure 8D and Figure 8E Describing sequential process stages of an operation according to disclosed embodiments;

[0017] Figure 9A 、 Figure 9B and Figure 9C Describing sequential process stages of an operation according to disclosed embodiments;

[0018] Figure 10A 、 Figure 10B 、 Figure 10C and Figure 10D Describing sequential process stages of an operation according to disclosed embodiments;

[0019] Figure 11A 、 Figure 11B and Figure 11CDescribe a sequential process stage of an operation according to the disclosed embodiments;

[0020] Figure 12A , Figure 12B , Figure 12C , Figure 12D , Figure 12E and Figure 12F Describe the process stages of sequential operations according to the disclosed embodiments;

[0021] Figure 13A and Figure 13B Describe a sequential process stage of an operation according to the disclosed embodiments;

[0022] Figure 14A , Figure 14B , Figure 14C and Figure 14D Describe a sequential process stage of an operation according to the disclosed embodiments;

[0023] Figure 15A and Figure 15B Describe a sequential process stage of an operation according to the disclosed embodiments;

[0024] Figure 16A , Figure 16B and Figure 16C Describe the process stages of sequential operations according to the disclosed embodiments;

[0025] Figure 17A , Figure 17B and Figure 17C Describe the process stages of sequential operations according to the disclosed embodiments;

[0026] Figure 18A and Figure 18B Describe the process stages of sequential operations according to the disclosed embodiments;

[0027] Figure 19 Describe a sequential process stage of an operation according to the disclosed embodiments;

[0028] Figure 20 Describe examples of radical inhibitors according to the disclosed embodiments;

[0029] Figure 21 Describe examples of thermal radical inhibitors according to the disclosed embodiments;

[0030] Figure 22A and Figure 22B Describe examples of photo radical inhibitors according to the disclosed embodiments;

[0031] Figure 23A , Figure 23B and Figure 23C Describe organometallic precursors according to the disclosed embodiments;

[0032] Figure 24 Describe a photoresist deposition apparatus according to the disclosed embodiments;

[0033] Figure 25 Describe the reaction of a photoresist layer upon exposure to actinic radiation and heating according to the disclosed embodiments;

[0034] Figure 26A 、 Figure 26B 、 Figure 26C 、 Figure 26D 、 Figure 26E and Figure 26F Describe a sequential process stage of an operation according to the disclosed embodiments;

[0035] Figure 27 Describe the process stages of sequential operations according to the disclosed embodiments;

[0036] Figure 28 Describe the process stages of sequential operations according to the disclosed embodiments;

[0037] Figure 29A and Figure 29B Describe the process stages of sequential operations according to the disclosed embodiments;

[0038] Figure 30A and Figure 30B Describe the process stages of sequential operations according to the disclosed embodiments;

[0039] Figure 31 Describe the process stages of sequential operations according to the disclosed embodiments;

[0040] Figure 32 Describe the process stages of sequential operations according to the disclosed embodiments.

[0041]

Symbol Description

[0042] 10: Substrate

[0043] 15: Photoresist layer

[0044] 19: Additive

[0045] 20: Underlayer

[0046] 20': Underlayer

[0047] 20a: Bottom layer

[0048] 20b: Intermediate layer

[0049] 21: Heater

[0050] 22: Photoresist structure

[0051] 25': Top layer

[0052] 25: Top layer

[0053] 30: Photomask

[0054] 35: Opaque pattern

[0055] 40: Photomask substrate

[0056] 45: Actinic radiation

[0057] 50: Exposed portion

[0058] 52: Unexposed portion

[0059] 55: Opening pattern

[0060] 55': Concave pattern

[0061] 55”: Pattern

[0062] 55”': Pattern

[0063] 57: Developer

[0064] 58: Developer

[0065] 60: Target layer

[0066] 62: Dispenser

[0067] 65: Reflective photomask

[0068] 70: Low thermal expansion glass substrate

[0069] 75: Reflective multilayer

[0070] 80: Overlayer

[0071] 85: Absorbing layer

[0072] 90: Backside conductive layer

[0073] 95: Extreme ultraviolet radiation

[0074] 97: Extreme ultraviolet radiation

[0075] 100: Method

[0076] 105: Dry developer

[0077] 200: Deposition apparatus

[0078] 205: Vacuum chamber

[0079] 210: Substrate support stage

[0080] 220: Compound gas supply

[0081] 225: Carrier / rinse gas supply

[0082] 230: Inlet

[0083] 230': Inlet

[0084] 235: Gas pipeline

[0085] 235': Gas pipeline

[0086] 240: Compound gas supply

[0087] 245: Vacuum pump

[0088] 250: Outlet

[0089] 255: Exhaust pipeline

[0090] 260: Controller

[0091] 300: Method

[0092] 400: Method

[0093] 500: Method

[0094] S110: Operation

[0095] S120: Operation

[0096] S130: Operation

[0097] S140: Operation[[ID=4�]]

[0098] S150: Operation

[0099] S160: Operation

[0100] S170: Operation

[0101] S210: Operation

[0102] S220: Operation

[0103] S230: Operation

[0104] S240: Operation

[0105] S250: Operation

[0106] S260: Operation

[0107] S270: Operation

[0108] S280: Operation

[0109] S290: Operation

[0110] S310: Operation

[0111] S320: Operation

[0112] S330: Operation

[0113] S340: Operation

[0114] S350: Operation

[0115] S360: Operation

[0116] S370: Operation

[0117] S380: Operation

[0118] S410: Operation

[0119] S420: Operation

[0120] S430: Operation

[0121] S440: Operation

[0122] S450: Operation

[0123] S460: Operation

[0124] S470: Operation

[0125] S480: Operation

[0126] S510: Operation

[0127] S520: Operation

[0128] S530: Operation

[0129] S540: Operation

[0130] S550: Operation

[0131] S560: Operation Detailed Implementation Manner

[0132] It should be understood that the following disclosure provides many different embodiments or examples for implementing different features of the present disclosure. Specific embodiments or examples will be described below for components and configurations to simplify the current disclosure. Of course, these are only examples and are not intended to be limiting. For example, the dimensions of the components are not limited to the ranges or values disclosed, but may depend on the manufacturing process conditions and / or required properties of the device. In addition, in the following description of the first feature being formed above the second feature, there may be embodiments where the first feature and the second feature are in direct contact to form, and there may also be embodiments where other features may be formed between the first feature and the second feature, such that the first feature and the second feature may not be in direct contact. For simplicity and clarity, the various features may be drawn at arbitrary scales.

[0133] In addition, relative space terms, such as below and above, etc., can facilitate the description here of the relationship between one element or feature and another element or feature shown in the figure. In addition to the directions described in the figure, relative space terms are intended to cover different directions of the device during use or operation. The device may be positioned in other ways (rotated 90 degrees or in other directions), and the relative space descriptions used here can be correspondingly interpreted in the same way. In addition, the term "made of" may mean "including" or "comprising".

[0134] With the pursuit of higher device density, higher performance, and lower cost, the semiconductor industry has advanced towards the nodes of nanofabrication technologies, posing challenges to reducing the feature size of semiconductors. Extreme ultraviolet lithography (EUVL) has been developed to form smaller semiconductor device feature sizes and increase the device density on semiconductor wafers. To improve EUVL, it is necessary to increase the exposure dose of the wafer. The exposure dose of the wafer can be improved by increasing the exposure intensity or the photosensitivity of the photoresist.

[0135] Highly charged tin ions are the atomic source of narrow-band extreme ultraviolet (EUV) light at a wavelength of 13.5 nm in nano-lithography. Hydrogen is introduced into the EUVL process to reduce mirror damage caused by tin (Sn) droplets. Hydrogen reacts with tin to form gaseous stannane (SnH4). However, EUV radiation can act on hydrogen to form hydrogen radicals. These hydrogen radicals can react with the photoresist on the wafer with a photoresist coating during the lithography process. This may cause degradation during the photoresist patterning operation, resulting in defects and an increase in line width roughness (LWR).

[0136] In some embodiments, the photoresist layer is treated with an additive to inhibit or prevent degradation of the photoresist caused by free radicals such as hydrogen radicals. In some embodiments, the additive is injected, treated, doped, or copolymerized into the photoresist layer. In some embodiments, the additive is injected, treated, doped, or copolymerized into the underlying layer below or the top layer above the photoresist layer. In some embodiments, the additive is added to the photoresist developer composition and introduced into the photoresist during the development operation. In some embodiments, the additive is mixed into a solvent; the mixture is applied to the photoresist underlying layer, the photoresist layer, or the photoresist top layer; and the additive diffuses into each of the photoresist underlying layer, the photoresist layer, or the photoresist top layer. In some embodiments, the underlying layer includes the bottom layer and the intermediate layer of a three-layer photoresist. In some embodiments, the additive is introduced into the intermediate layer of the three-layer photoresist, which includes a bottom layer and an upper photosensitive layer.

[0137] In some embodiments, the additive is one or more selected from the group consisting of (A) a radical inhibitor, (B) a thermal radical inhibitor, and (C) a photo radical inhibitor. The additive can terminate the reaction of hydrogen radicals or other types of radicals.

[0138] Figures 1 to 5 The manufacturing process flow of a semiconductor device is described according to the disclosed embodiments.

[0139] As Figure 1 shown, method 100 for manufacturing a semiconductor device includes an operation S110 of forming an underlying layer 20 on a substrate 10 by coating an underlying composition on the substrate 10 (see Figure 6A , Figure 6B , Figure 7A and Figure 8A ). In some embodiments, the underlying layer 20 is a layer with a bottom anti-reflective coating (BARC). In some embodiments, the underlying composition includes an additive to inhibit or prevent radicals such as hydrogen radicals from degrading the photoresist. In some embodiments, the additive is then added to the underlying layer 20 in operation S120 (see Figure 8B ). Then, a photoresist composition is coated on the underlying layer 20 in operation S130 to form a photoresist structure including the underlying layer 20 and a photoresist layer 15 (see Figure 6A , Figure 6B , Figure 7B and Figure 8D ). In some embodiments, the photoresist is a metal-containing photoresist formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD). In other embodiments, the metal-containing photoresist layer is formed by a spin coating method.

[0140] In some embodiments, the photoresist layer 15 undergoes a pre-exposure bake (or a first heating operation) in operation S140 after the photoresist layer 15 is formed. In some embodiments, the first heating operation S140 includes heating the photoresist layer 15 at a temperature between about 40 degrees Celsius and about 150 degrees Celsius for about 10 seconds to about 10 minutes. In some embodiments, the first heating operation S140 causes the additive to diffuse from the underlying layer 20 into the photoresist layer 15. In some embodiments, the additive diffuses throughout the photoresist layer 15. In some embodiments, the additive diffuses uniformly throughout the photoresist layer 15. In other embodiments, the additive diffuses into the photoresist layer such that the additive forms a concentration gradient with the highest concentration at the photoresist layer 15 / underlying layer 20 interface.

[0141] Next, the photoresist layer 15 is selectively exposed to actinic radiation 45 / extreme ultraviolet (EUV) radiation 97 in operation S150 (see [[ID= and ​ ). In some embodiments, the photoresist layer 15 is a photoresist layer. In some embodiments, the photoresist layer 15 is selectively or patternedly exposed to ultraviolet (UV) radiation. In some embodiments, the UV radiation is deep ultraviolet (DUV) radiation. In some embodiments, the UV radiation is extreme ultraviolet (EUV) radiation. In some embodiments, the photoresist layer 15 is selectively or patternedly exposed to an electron beam.

[0142] According to the present disclosure, a photoresist layer is a layer that undergoes a chemical reaction upon absorption of actinic radiation, causing the portion of the photoresist layer exposed to actinic radiation to change its solubility in a developer and form a contrast with the portion of the photoresist layer not exposed to actinic radiation. A layer that is not photosensitive to actinic radiation will not substantially undergo a chemical reaction upon exposure to actinic radiation to change its solubility in the developer.

[0143] As ​ shown, in some embodiments, the actinic radiation 45 is irradiated through a photomask 30 onto the photoresist layer 15. In some embodiments, the photomask 30 has a pattern to be replicated on the photoresist layer 15. In some embodiments, this pattern is formed by an opaque pattern 35 on a photomask substrate 40. The opaque pattern 35 may be formed of a material that is opaque to UV radiation, such as chromium; and the photomask substrate 40 is formed of a material that is transparent to UV radiation, such as fused silica.

[0144] In some embodiments, extreme ultraviolet (EUV) lithography is used to selectively or patternedly expose the photoresist layer 15 to form exposed portions 50 and unexposed portions 52. In an EUV lithography operation, a reflective mask 65 is used to form patterned exposure light rays in some embodiments, such as ​ shown. The reflective mask 65 includes a low thermal expansion glass substrate 70 having a reflective multilayer 75 formed of silicon and molybdenum on top. A cover layer 80 and an absorber layer 85 are formed on the reflective multilayer 75. A backside conductive layer 90 is formed on the back of the low thermal expansion glass substrate 70. The EUV radiation 95 is incident on the reflective mask 65 at an incident angle of approximately 6 degrees. A portion of the EUV radiation 97 is reflected by the reflective multilayer 75 onto the substrate 10 with a photoresist coating, while the portion of the EUV radiation incident on the absorber layer 85 is absorbed by the mask. In some embodiments, additional optical elements including mirrors are disposed between the reflective mask 65 and the substrate 10 with a photoresist coating.

[0145] In some embodiments, a substrate having a photoresist coating is placed in a lithography process for exposure to radiation. The lithography process includes a photomask 30, a reflective photomask 65, optical elements, a radiation source for providing exposure of actinic radiation 45 / extreme ultraviolet (EUV) radiation 97, and a movable stage for supporting and moving the substrate under the exposure radiation.

[0146] In some embodiments, the lithography process uses optical elements (not shown) to expand, reflect, or otherwise control the radiation before or after patterning the actinic radiation 45 / EUV radiation 97 with the photomask 30 / reflective photomask 65. In some embodiments, the optical elements include one or more lenses, mirrors, filters, and combinations thereof to control the actinic radiation 45 / EUV radiation 97 along the path of the actinic radiation 45 / EUV radiation 97.

[0147] In some embodiments, the radiation is electromagnetic radiation, such as g-line (wavelength of approximately 436 nm), i-line (wavelength of approximately 365 nm), ultraviolet radiation, far ultraviolet radiation, extreme ultraviolet light, electron beam, etc. In some embodiments, the radiation source is preferably selected from the group consisting of a mercury lamp, a xenon lamp, a carbon arc lamp, a krypton fluoride excimer laser (wavelength 248 nm), an argon fluoride excimer laser (wavelength 193 nm), a fluorine excimer laser (wavelength 157 nm), or a carbon dioxide laser-excited tin plasma (EUV wavelength of 13.5 nm).

[0148] The amount of electromagnetic radiation can be obtained as a fluence or dose by integrating the radiation flux over the exposure time. In some embodiments, suitable radiation fluence ranges from about 1 mJ / cm 2 to about 150 mJ / cm 2 , in other embodiments from about 2 mJ / cm 2 to about 100 mJ / cm 2 , and in other embodiments from about 3 mJ / cm 2 to about 50 mJ / cm 2 . Those of ordinary skill in the art will recognize that other radiation fluence ranges within the above-specified ranges are contemplated and are encompassed by this disclosure.

[0149] In some embodiments, selective or patterned exposure is performed by scanning an electron beam. Through electron beam lithography, the electron beam induces secondary electrons to modify the irradiated material. High resolution can be achieved using electron beam lithography and the metal-containing photoresists disclosed herein. In some embodiments, the electron beam can be characterized by the energy of the beam, and suitable energy ranges from about 5 volts to about 200 kilovolts (kV), and in other embodiments from about 7.5 volts to about 100 kV. In some embodiments, the dose range of a proximity correction beam of 30 kV ranges from about 0.1 μC / cm2 to about 5 μC / cm 2 In some embodiments, and in other embodiments from about 0.5 μC / cm 2 to about 1 μC / cm 2 and in other embodiments from about 1 μC / cm 2 to about 100 μC / cm 2 One of ordinary skill in the art can calculate the corresponding doses for other beam energies based on the teachings herein, and should recognize that other ranges of electron beam properties within the explicit ranges above are contemplated and are encompassed by this disclosure.

[0150] In some embodiments, the exposure of the photoresist layer 15 uses immersion lithography techniques. In this technique, an immersion medium (not shown) is placed between the final optical element and the photoresist layer, such that actinic radiation 45 exposes the photoresist layer 15 through the immersion medium.

[0151] The exposed portion 50 of the photoresist layer exposed to radiation undergoes a chemical reaction, thereby changing its sensitivity such that it is removed in a subsequent development operation S170. In some embodiments, the exposed portion 50 of the photoresist layer exposed to radiation reacts such that the exposed portion is more easily removed in the development operation S150. In other embodiments, the exposed portion 50 of the photoresist layer exposed to radiation reacts such that the exposed portion is resistant to removal in the development operation S150.

[0152] Next, the photoresist layer 15 undergoes a second heating or post - exposure bake (PEB) in operation S160. In some embodiments, the photoresist layer 15 is heated at a temperature from about 50 degrees Celsius to about 250 degrees Celsius for about 20 seconds to about 300 seconds. In some embodiments, the post - exposure bake temperature ranges from about 100 degrees Celsius to about 230 degrees Celsius, and in other embodiments from about 150 degrees Celsius to about 200 degrees Celsius. In some embodiments, the post - exposure bake operation S160 causes cross - linking of the reaction product of a first compound or first precursor and a second compound or second precursor in the photoresist layer.

[0153] The selectively exposed photoresist layer 15 is then developed in operation S170. In some embodiments, the photoresist layer 15 is developed by applying a solvent - based developer 57 to the selectively exposed photoresist layer. As ​ shown, the liquid developer 57 is supplied from a dispenser 62 to the photoresist layer 15. In some embodiments, the exposed portion 50 of the photoresist layer undergoes a cross - linking reaction due to exposure to actinic radiation or post - exposure bake, while the unexposed portion 52 of the photoresist layer is removed by the developer 57 to form an opening pattern 55 in the photoresist layer 15, thereby exposing the substrate 10, as​ As shown. In some embodiments, the photoresist layer 15 disposed under the non-exposed portion 52 of the photoresist layer is removed during the development operation.

[0154] In some embodiments, the developer 57 for the photoresist includes a solvent and an acid or a base. In some embodiments, based on the total weight of the developer for the photoresist, the concentration of the solvent ranges from about 60 wt% to about 99 wt%. Based on the total weight of the developer for the photoresist, the concentration of the acid or the base ranges from about 0.001 wt% to about 20 wt%. In some embodiments, based on the total weight of the developer, the concentration of the acid or the base in the developer ranges from about 0.01 wt% to about 15 wt%.

[0155] In some embodiments, the developer 57 is applied to the photoresist layer 15 using a spin coating process. In the spin coating process, when the substrate with the photoresist coating is rotating, the developer 57 is applied to the photoresist layer 15 from above the photoresist layer 15, as ​ shown. In some embodiments, the supply rate of the developer 57 is between about 5 milliliters per minute and about 800 milliliters per minute, and the rotation speed of the substrate 10 with the photoresist coating is between about 100 revolutions per minute and about 2000 revolutions per minute. In some embodiments, the temperature of the developer is between about 10 degrees Celsius and about 80 degrees Celsius. In some embodiments, the development operation lasts for about 30 seconds to about 10 minutes.

[0156] In some embodiments, the developer 57 includes an organic solvent. The organic solvent can be any suitable solvent. In some embodiments, the solvent is selected from one or more of the group consisting of propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, 4-methyl-2-pentanol, acetone, methyl ethyl ketone, dimethylformamide (DMF), isopropanol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (MIBC), n-butyl acetate (nBA), 2-heptanone (MAK), and dioxane.

[0157] Although the spin coating operation is one of the suitable methods for developing the photoresist layer 15 after exposure, it is intended to illustrate rather than limit the embodiments. Conversely, any suitable developing operation, including immersion processes, puddle processes, and spray methods, can alternatively be used. All of these developing operations are included within the scope of the embodiments.

[0158] In some embodiments, a dry developer 105 is applied to the selectively exposed photoresist layer 15, as ​ 、 ​ and ​ shown. In some embodiments, the dry developer 105 is a plasma or a chemical gas, and the dry developing operation S170 is a plasma etching or chemical etching operation. Dry development uses differences related to the composition, degree of crosslinking, and film density to selectively remove the portions of the photoresist layer that are desired to be removed. In some embodiments, the dry development process uses a mild plasma (high voltage, low power) or a thermal process in a heated vacuum chamber when flowing gaseous dry developing chemicals, such as flowing boron trichloride, boron trifluoride, or other Lewis acids. In some embodiments, boron trichloride removes the unexposed material, leaving the pattern of the exposed film and transferring it to the underlying layer through a plasma-based etching process.

[0159] In some embodiments, dry development includes plasma processes, including transformer-coupled plasma (TCP), inductively coupled plasma (ICP), or capacitively coupled plasma (CCP). In some embodiments, the plasma process is carried out in a pressure range of about 5 mTorr to about 20 mTorr, at a power level of about 250 W to about 1000 W, in a temperature range of about 0 °C to about 300 °C, and at a flow rate of about 100 sccm to about 1000 sccm for about 1 second to 3000 seconds.

[0160] In some embodiments, the photoresist is a negative photoresist, and the unexposed portion 52 of the photoresist layer 15 is removed in the developing operation S170 to provide an opening pattern 55 in the exposed portion of the photoresist layer on the substrate 10, as ​ shown. In other embodiments, the photoresist is a positive photoresist, and the exposed portion 50 of the photoresist layer 15 is removed in the developing operation S170. After the developing operation, other processes are carried out when the patterned photoresist layer 15 / exposed portion 50 is in place. For example, in some embodiments, an etching operation is carried out using dry etching or wet etching to transfer the opening pattern 55 of the photoresist layer 15 / exposed portion 50 to the underlying substrate 10 to form a recessed pattern 55', as ​As shown. The substrate 10 has an etching resistance different from that of the photoresist layer 15. In some embodiments, the etchant is more selective for the substrate 10 than for the photoresist layer 15. In some embodiments, the patterned photoresist layer 15 / exposed portion 50 is at least partially removed during the etching operation in certain embodiments. In other embodiments, the patterned photoresist layer 15 / exposed portion 50 is removed after etching the substrate 10 by selectively etching, using a suitable photoresist stripping solvent, or by a photoresist plasma ashing operation.

[0161] In other embodiments, as ​ shown, the deposition apparatus 200 for manufacturing a semiconductor device selectively includes an operation S210 of forming an underlying layer 20 including a bottom layer 20a and an intermediate layer 20b on the substrate 10 (see ​ ), this formation is by coating a bottom layer composition on the substrate 10 and then by coating an intermediate layer composition on the bottom layer 20a. In some embodiments, a photoresist composition is then coated on the underlying layer 20 in operation S220 to form the photoresist layer 15 (see ​ , ​ , ​ and ​ ). In some embodiments, a heating (or baking) operation is performed after coating the bottom layer composition and / or after coating the intermediate layer composition. In some embodiments, the photoresist is a metal-containing photoresist formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD). In other embodiments, the metal-containing photoresist layer is formed by a spin coating method.

[0162] In some embodiments, an operation S230 of pre-exposure baking (or first heating operation) is performed on the photoresist layer 15 after the photoresist layer 15 is formed. In some embodiments, the first heating operation S230 includes heating the photoresist layer 15 at a temperature between about 40 degrees Celsius and about 150 degrees Celsius for about 10 seconds to about 10 minutes.

[0163] In some embodiments, the top layer 25 can be selectively formed on the photoresist layer 15 in operation S240 (see ​ ), by coating a top layer composition on the photoresist layer 15 to form a photoresist structure including the top layer 25 and the photoresist layer. In some embodiments, the top layer composition includes an additive to inhibit or prevent degradation of the photoresist caused by radicals such as hydrogen radicals. In other embodiments, the additive is subsequently added to the top layer 25 in operation S250 (see ​ ).

[0164] The operation S260 of the second baking or heating is then carried out in some embodiments. The operation S260 of the second heating causes the additive to diffuse from the top layer 25 into the photoresist layer 15. In some embodiments, the additive diffuses throughout the photoresist layer 15. In some embodiments, the additive diffuses uniformly throughout the photoresist layer 15. In other embodiments, the additive diffuses into the photoresist layer to form a concentration gradient, with the highest concentration at the interface of the photoresist layer 15 / top layer 25.

[0165] The photoresist layer 15 and the top layer 25 are then selectively exposed to actinic radiation 45 / extreme ultraviolet radiation 97 in operation S270 (see ​ and ​ ). In some embodiments, the photoresist layer 15 and the top layer 25 are selectively or patternedly 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 15 is selectively or patternedly exposed to an electron beam. In some embodiments, the photoresist layer 15 is a photoresist layer that is photosensitive to actinic radiation 45 / extreme ultraviolet radiation 97. In some embodiments, the actinic radiation 45 / extreme ultraviolet radiation 97 is substantially not absorbed by the top layer 25.

[0166] As ​ shown, in some embodiments, the actinic radiation 45 passes through the photomask 30 before irradiating and exposing the photoresist layer 15 and the top layer 25. In some embodiments, extreme ultraviolet lithography is used to selectively or patternedly expose the photoresist layer 15 to form an exposed portion 50 and an unexposed portion 52. In the extreme ultraviolet lithography operation, a reflective photomask 65 is used in some embodiments to form patterned exposure light rays, as ​ shown. The photomask, exposure radiation, and exposure conditions here are the same as those described in method 100 and operation S150.

[0167] Next, the photoresist layer 15 is subjected to a post-exposure bake (PEB) in operation S280. In some embodiments, the photoresist layer 15 is heated at a temperature of about 50 degrees Celsius to about 250 degrees Celsius for about 20 seconds to about 300 seconds. In some embodiments, the temperature of the post-exposure bake ranges from about 100 degrees Celsius to about 230 degrees Celsius, and in other embodiments, the temperature ranges from about 150 degrees Celsius to about 200 degrees Celsius. In some embodiments, the operation S280 of the post-exposure bake causes the reaction product of the first compound or the first precursor and the second compound or the second precursor in the photoresist layer to crosslink.

[0168] The selectively exposed photoresist layer 15 and the top layer 25 are then developed in operation S290. In some embodiments, the photoresist layer 15 is developed by applying a solvent-based developer 57 to the selectively exposed photoresist layer. As ​ shown, the liquid developer 57 is supplied from the dispenser 62 to the top layer 25 and the photoresist layer 15. In some embodiments, the photoresist is a negative photoresist, and the exposed portion 50 of the photoresist layer undergoes a crosslinking reaction due to exposure to actinic radiation or post-exposure baking, while the unexposed portion 52 of the photoresist layer is removed by the developer 57, thereby forming an opening pattern 55 in the photoresist layer 15, and further exposing the substrate 10, as ​ shown. In some embodiments, the top layer 25 is removed during the development operation. In some embodiments, a dry developer 105 is applied to the selectively exposed photoresist layer 15 and the top layer 25, as ​ shown. Here, the development conditions and parameters of operation S290 are the same as those disclosed in operation S170 in some embodiments of method 100.

[0169] The development operation S290 provides an opening pattern 55 in the portion of the photoresist layer that exposes the substrate 10, as ​ shown. After the development operation, other processes are performed when the patterned photoresist layer 15 / exposed portion 50 is in place. For example, in some embodiments, an etching operation is performed using dry etching or wet etching to transfer the opening pattern 55 of the photoresist layer 15 / exposed portion 50 to the underlying substrate 10 to form a recessed pattern 55', as ​ shown. The substrate 10 has different etching resistance from the photoresist layer 15. In some embodiments, the etchant is more selective for the substrate 10 than for the photoresist layer 15. In some embodiments, the patterned photoresist layer 15 / exposed portion 50 is at least partially removed during the etching operation in some embodiments. In other embodiments, after etching the substrate 10, the patterned photoresist layer 15 / exposed portion 50 is removed by selectively etching, using a suitable photoresist stripping solvent, or by a photoresist plasma ashing operation.

[0170] Another disclosed embodiment is as ​ shown. The method 300 for manufacturing a semiconductor device selectively includes an operation S310 of forming a bottom layer 20 including a bottom layer 20a and an intermediate layer 20b on the substrate 10 (see ​ ), and this formation is achieved by coating a bottom layer composition on the substrate 10 and then coating an intermediate layer composition on the bottom layer 20a. In some embodiments, a photoresist composition is then coated on the bottom layer 20 in operation S320 to form a photoresist layer 15 (see ​ , ​ , ​ and ​In some embodiments, a heating (or baking) operation is performed after coating the bottom layer composition and / or after coating the intermediate layer composition. In some embodiments, the photoresist is a metal-containing photoresist formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD). In other embodiments, the metal-containing photoresist layer is formed by spin coating.

[0171] In some embodiments, the photoresist layer 15 undergoes a pre-exposure bake operation S330 (or a first heating operation) after the photoresist layer 15 is formed. In some embodiments, the first heating operation S330 includes heating the photoresist layer 15 at a temperature between about 40 degrees Celsius and about 150 degrees Celsius for about 10 seconds to about 10 minutes.

[0172] The photoresist layer 15 is then selectively exposed to actinic radiation 45 / EUV radiation 97 in operation S340 (see ​ and ​ In some embodiments, 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). In some embodiments, photoresist layer 15 is selectively or patterned exposed to an electron beam. In some embodiments, photoresist layer 15 is a photoresist layer that is sensitive to actinic radiation 45 / EUV radiation 97.

[0173] like ​ As shown, in some embodiments, actinic radiation 45 passes through a mask 30 before being applied to the exposed photoresist layer 15. In some embodiments, EUV lithography is used to selectively or pattern-wise expose the photoresist layer 15 to form exposed portions 50 and unexposed portions 52. In the EUV lithography operation, a reflective mask 65 is used to form a patterned exposure light in some embodiments, such as ​ The photomask, exposure radiation, and exposure conditions are the same as those in operation S150 described in method 100 .

[0174] The top layer 25 is then in operation S350 (see ​ and ​) is formed on the selectively or patterned exposed photoresist layer 15 by coating a top layer composition on the photoresist layer 15. In some embodiments, the top layer composition includes additives to inhibit or prevent radicals such as hydrogen radicals from causing photoresist degradation. In other embodiments, the additives are then added to the top layer 25' in operation S360 (see ​ ).

[0175] In some embodiments, post exposure baking (PEB) is then performed in operation S370. In some embodiments, the photoresist layer 15 is heated at a temperature of about 50 degrees Celsius to about 250 degrees Celsius for about 20 seconds to about 300 seconds. In some embodiments, the post exposure baking is performed in a temperature range of about 100 degrees Celsius to about 230 degrees Celsius, and in other embodiments in a temperature range of about 150 degrees Celsius to about 200 degrees Celsius. In some embodiments, the operation S370 of post exposure baking crosslinks the reaction product of the first compound or the first precursor and the second compound or the second precursor in the photoresist layer. In addition to further promoting the reaction of the photoresist layer 15 exposed to actinic radiation, the operation S370 of post exposure baking also causes the additives to diffuse from the top layer 25 into the photoresist layer 15. In some embodiments, the additives diffuse throughout the photoresist layer 15. In some embodiments, the additives diffuse uniformly throughout the photoresist layer 15. In other embodiments, the additives diffuse into the photoresist layer to form a concentration gradient and have the highest concentration at the interface of the photoresist layer 15 / top layer 25.

[0176] The selectively exposed photoresist layer 15 and the top layer 25 are then developed in operation S380. In some embodiments, the photoresist layer 15 is developed by applying a solvent-based developer 57 to the selectively exposed photoresist layer. As ​ shown, the liquid developer 57 is supplied from the dispenser 62 to the top layer 25 and the photoresist layer 15. In some embodiments, the photoresist is a negative photoresist, and the exposed portion 50 of the photoresist layer undergoes a crosslinking reaction due to exposure to actinic radiation or post exposure baking, while the unexposed portion 52 of the photoresist layer is removed by the developer 57, thereby forming an opening pattern 55 in the photoresist layer 15, and further exposing the substrate 10, as ​ shown. In some embodiments, the top layer 25 is removed during the developing operation. In some embodiments, a dry developer 105 is applied to the selectively exposed photoresist layer 15 and the top layer 25, as ​ shown. The developing conditions and parameters of operation S380 here are the same as those of operation S170 of method 100 in some of the disclosed embodiments.

[0177] The developing operation S380 provides an opening pattern 55 in the portion of the photoresist layer exposing the substrate 10, as​ As shown. After the development operation, other processes are performed when the patterned photoresist layer 15 / exposed portion 50 is in place. For example, in some embodiments, an etching operation is performed using dry etching or wet etching to transfer the pattern of the photoresist layer 15 / exposed portion 50 to the underlying substrate 10 to form a recessed pattern 55', as ​ shown. The substrate 10 has different etching resistance from the photoresist layer 15. In some embodiments, the etchant is more selective for the substrate 10 than for the photoresist layer 15. In some embodiments, the patterned photoresist layer 15 / exposed portion 50 is at least partially removed during the etching operation in some embodiments. In other embodiments, after etching the substrate 10, the patterned photoresist layer 15 / exposed portion 50 is removed by selectively etching, using a suitable photoresist stripping solvent, or by a photoresist plasma ashing operation.

[0178] Another disclosed embodiment is as ​ shown. The method 400 for manufacturing a semiconductor device selectively includes an operation S410 of forming an underlying layer 20 including a bottom layer 20a and an intermediate layer 20b on the substrate 10 (see ​ ), this formation is by coating the bottom layer composition on the substrate 10, and then by coating the intermediate layer composition on the bottom layer 20a. In some embodiments, a photoresist composition is then coated on the underlying layer 20 in operation S420 to form the photoresist layer 15 (see ​ , ​ , ​ and ​ ). In some embodiments, a heating (or baking) operation is performed after coating the bottom layer composition and / or after coating the intermediate layer composition. In some embodiments, the photoresist is a metal-containing photoresist formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD). In other embodiments, the metal-containing photoresist layer is formed by a spin coating method.

[0179] In some embodiments, the photoresist layer 15 is subjected to a pre-exposure bake (or a first heating operation) in operation S430 after the photoresist layer 15 is formed. In some embodiments, the first heating operation S430 includes heating the photoresist layer 15 at a temperature between about 40 degrees Celsius and about 150 degrees Celsius for about 10 seconds to about 10 minutes.

[0180] The photoresist layer 15 is then selectively exposed to actinic radiation 45 / extreme ultraviolet radiation 97 in operation S440 (see ​ and ​)。In some embodiments, the photoresist layer 15 is selectively or patternwise 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 15 is selectively or patternwise exposed to an electron beam. In some embodiments, the photoresist layer 15 is a photoresist layer that is photosensitive to actinic radiation 45 / extreme ultraviolet radiation 97.

[0181] As ​ shown, in some embodiments, the actinic radiation 45 passes through the photomask 30 before irradiating and exposing the photoresist layer 15. In some embodiments, extreme ultraviolet lithography is used to selectively or patternwise expose the photoresist layer 15 to form an exposed portion 50 and an unexposed portion 52. In the extreme ultraviolet lithography operation, a reflective photomask 65 is used to form patterned exposure light rays in some embodiments, as ​ shown. The photomask, exposure radiation, and exposure conditions here are the same as those described in method 100 and operation S150.

[0182] The post exposure baking (PEB) operation S450 is then performed in some embodiments. In some embodiments, the photoresist layer 15 is heated at a temperature of about 50 degrees Celsius to about 250 degrees Celsius for about 20 seconds to about 300 seconds. In some embodiments, the post exposure baking is performed in a temperature range of about 100 degrees Celsius to about 230 degrees Celsius, and in other embodiments, in a temperature range of about 150 degrees Celsius to about 200 degrees Celsius. In some embodiments, the post exposure baking operation S450 crosslinks the reaction product of the first compound or first precursor and the second compound or second precursor in the photoresist layer.

[0183] The top layer 25 is then formed in operation S460 (see ​ and ​ ) on the selectively or patternwise exposed and post exposure baked photoresist layer 15 by coating a top layer composition on the photoresist layer 15. In some embodiments, the top layer composition includes additives to inhibit or prevent degradation of the photoresist caused by free radicals such as hydrogen radicals. In other embodiments, the additives are then added to the top layer 25 during the operation.

[0184] The top layer 25 and the photoresist layer 15 then undergo a third baking operation S470 to allow the additive to diffuse from the top layer 25 into the photoresist layer 15. In some embodiments, the additive diffuses throughout the photoresist layer 15. In some embodiments, the additive diffuses evenly throughout the photoresist layer 15. In other embodiments, the additive diffuses into the photoresist layer to form a concentration gradient and has the highest concentration at the interface of the photoresist layer 15 / top layer 25. In some embodiments, the third baking operation S470 includes heating the top layer 25 and the photoresist layer 15 at a temperature between approximately 40 degrees Celsius and approximately 150 degrees Celsius for approximately 10 seconds to approximately 10 minutes.

[0185] The selectively exposed photoresist layer 15 and the top layer 25 are then developed in operation S480. In some embodiments, the photoresist layer 15 is developed by applying a solvent-based developer 57 to the selectively exposed photoresist layer. As ​ shown, the liquid developer 57 is supplied from the dispenser 62 to the top layer 25 and the photoresist layer 15. In some embodiments, the exposed portion 50 of the photoresist layer undergoes a crosslinking reaction due to exposure to actinic radiation or post-exposure baking, while the unexposed portion 52 of the photoresist layer is removed by the developer 57 to form an opening pattern 55 in the photoresist layer 15, thereby exposing the substrate 10, such as ​ shown. In some embodiments, the top layer 25 is removed during the development operation. In some embodiments, a dry developer 105 is applied to the selectively exposed photoresist layer 15 and the top layer 25, as ​ shown. The development conditions and parameters of operation S480 here are the same as those of operation S170 of method 100 in some of the disclosed embodiments.

[0186] The development operation S480 provides an opening pattern 55 in the portion of the photoresist layer of the exposed substrate 10, as ​ shown. After the development operation, other processes are performed when the patterned photoresist layer 15 / exposed portion 50 is in place. For example, in some embodiments, an etching operation is performed using dry etching or wet etching to transfer the opening pattern 55 of the photoresist layer 15 / exposed portion 50 to the underlying substrate 10 to form a recessed pattern 55', as ​ shown. The substrate 10 has different etching resistance from the photoresist layer 15. In some embodiments, the etchant is more selective for the substrate 10 than for the photoresist layer 15. In some embodiments, the patterned photoresist layer 15 / exposed portion 50 is at least partially removed during the etching operation in some embodiments. In other embodiments, after etching the substrate 10, the patterned photoresist layer 15 / exposed portion 50 is removed by selectively etching, using a suitable photoresist stripping solvent, or by a photoresist plasma ashing operation.

[0187] Another disclosed embodiment is as ​As shown. The method 500 for manufacturing a semiconductor device selectively includes an operation S510 of forming a bottom layer 20 including a bottom layer 20a and an intermediate layer 20b on a substrate 10 (see ​ ), this formation is by coating a bottom layer composition on the substrate 10, and then by coating an intermediate layer composition on the bottom layer 20a. In some embodiments, a photoresist composition is then coated on the bottom layer 20 in operation S520 to form a photoresist layer 15 (see ​ , ​ , ​ and ​ ). In some embodiments, a heating (or baking) operation is performed after coating the bottom layer composition and / or after coating the intermediate layer composition. In some embodiments, the photoresist is a metal-containing photoresist formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD). In other embodiments, the metal-containing photoresist layer is formed by a spin coating method.

[0188] In some embodiments, the photoresist layer 15 is subjected to a pre-exposure bake (or a first heating operation) in operation S530 after the photoresist layer 15 is formed. In some embodiments, the first heating operation S530 includes heating the photoresist layer 15 at a temperature between about 40 degrees Celsius and about 150 degrees Celsius for about 10 seconds to about 10 minutes.

[0189] The photoresist layer 15 is then selectively exposed to actinic radiation 45 / extreme ultraviolet radiation 97 in operation S540 (see ​ and ​ ). In some embodiments, the photoresist layer 15 is selectively or patternedly 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 15 is selectively or patternedly exposed to an electron beam. In some embodiments, the photoresist layer 15 is a photoresist layer that is photosensitive to actinic radiation 45 / extreme ultraviolet radiation 97.

[0190] As ​ shown, in some embodiments, the actinic radiation 45 passes through a photomask 30 before irradiating and exposing the photoresist layer 15. In some embodiments, extreme ultraviolet lithography is used to selectively or patternedly expose the photoresist layer 15 to form an exposed portion 50 and an unexposed portion 52. In the extreme ultraviolet lithography operation, a reflective photomask 65 is used to form patterned exposure light in some embodiments, as​ as shown. The photomask, exposure radiation, and exposure conditions here are the same as those in operation S150 of the described method 100.

[0191] In some embodiments, post exposure baking (PEB) is then performed in operation S550. In some embodiments, the photoresist layer 15 is heated at a temperature of about 50 degrees Celsius to about 250 degrees Celsius for about 20 seconds to about 300 seconds. In some embodiments, the post exposure baking is performed in a temperature range of about 100 degrees Celsius to about 230 degrees Celsius, and in other embodiments, in a temperature range of about 150 degrees Celsius to about 200 degrees Celsius. In some embodiments, operation S550 of the post exposure baking crosslinks the reaction product of the first compound or first precursor and the second compound or second precursor in the photoresist layer.

[0192] The selectively exposed photoresist layer 15 is then developed in operation S560. The photoresist layer 15 is developed by applying a solvent-based developer 58, which includes additives to inhibit or prevent photoresist degradation caused by free radicals such as hydrogen radicals to the selectively exposed photoresist layer. As ​ shown, the liquid developer 58 is supplied from the dispenser 62 to the top layer 25 and the photoresist layer 15. In some embodiments, the exposed portion 50 of the photoresist layer undergoes a crosslinking reaction due to exposure to actinic radiation or post exposure baking, while the unexposed portion 52 of the photoresist layer is removed by the developer 58 to form an opening pattern 55 in the photoresist layer 15, thereby exposing the substrate 10, as ​ shown.

[0193] In some embodiments, the photoresist developer 58 includes a solvent, additives, and an acid or a base. In some embodiments, based on the total weight of the photoresist developer, the concentration of the solvent is about 60 wt% to about 99 wt%. In some embodiments, based on the total weight of the developer, the concentration of the additives in the developer is about 0.001 wt% to about 40 wt%. In some embodiments, based on the total weight of the developer, the concentration of the additives in the developer is about 0.1 wt% to about 20 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%. In some embodiments, based on the total weight of the photoresist developer, the concentration of the acid or base in the developer is about 0.01 wt% to about 15 wt%. For developer compositions outside the disclosed range, the line width roughness may increase or the photoresist pattern may be underdeveloped.

[0194] In some embodiments, the developer 58 is applied to the photoresist layer 15 by a spin coating process. In the developing process, the developer 58 is applied to the photoresist layer 15 from above the photoresist layer while the substrate with the photoresist coating is rotating, as ​ shown. In some embodiments, the supply rate of the developer 58 is between about 5 milliliters per minute and about 800 milliliters per minute, and the rotation speed of the substrate 10 with the photoresist coating is between about 100 revolutions per minute and about 2000 revolutions per minute. In some embodiments, the temperature of the developer is between about 20 degrees Celsius and about 150 degrees Celsius. In some embodiments, the developing operation lasts for about 30 seconds to about 10 minutes.

[0195] In some embodiments, the developer 58 includes an organic solvent. The organic solvent can be any suitable solvent. In some embodiments, the solvent is selected from one or more of the group consisting of propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, 4-methyl-2-pentanol, acetone, methyl ethyl ketone, dimethylformamide (DMF), isopropanol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (MIBC), n-butyl acetate (nBA), 2-heptanone (MAK), and dioxane.

[0196] Although the spin coating operation is one of the suitable methods 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 spray methods, can alternatively be used. All of these developing operations are within the scope of the embodiments.

[0197] The developing operation S560 provides the opening pattern 55 in the photoresist layer portion of the exposed substrate 10, as ​As shown. After the development operation, other processes are performed when the patterned photoresist layer 15 / exposed portion 50 is in place. For example, in some embodiments, an etching operation is performed using dry etching or wet etching to transfer the pattern of the photoresist layer 15 / exposed portion 50 to the underlying substrate 10 to form a recessed pattern 55', as ​ shown. The substrate 10 has an etching resistance different from that of the photoresist layer 15. In some embodiments, the etchant is more selective for the substrate 10 than for the photoresist layer 15. In some embodiments, the patterned photoresist layer 15 / exposed portion 50 is at least partially removed during the etching operation in some embodiments. In other embodiments, after etching the substrate 10, the patterned photoresist layer 15 / exposed portion 50 is removed by selectively etching, using a suitable photoresist stripping solvent, or by a photoresist plasma ashing operation.

[0198] In some embodiments, at least the surface portion of the substrate 10 includes a single-crystalline semiconductor layer. The substrate 10 may include a single-crystalline semiconductor material, such as but not limited to silicon, germanium, silicon germanium, gallium arsenide, indium antimonide, gallium phosphide, gallium antimonide, aluminum indium arsenide, gallium indium arsenide, gallium antimonide phosphide, gallium arsenide antimonide, and indium phosphide. In some embodiments, the substrate 10 is the silicon layer of a silicon-on-insulator (SOI) substrate. In certain embodiments, the substrate 10 is made of crystalline silicon.

[0199] The substrate 10 may include one or more buffer layers (not shown) in the surface region. The buffer layer can gradually change the lattice constant from the lattice constant of the substrate to the lattice constant of the subsequently formed source / drain regions. The buffer layer can be formed by epitaxially growing a single-crystalline semiconductor material, such as but not limited to silicon, germanium, germanium tin, silicon germanium, gallium arsenide, indium antimonide, gallium phosphide, gallium antimonide, aluminum indium arsenide, gallium indium arsenide, gallium antimonide phosphide, gallium arsenide antimonide, gallium nitride, and indium phosphide. In an embodiment, a silicon germanium (SiGe) buffer layer is epitaxially grown on the silicon substrate 10. The germanium concentration of the silicon germanium buffer layer may increase from 30 atomic percent in the bottommost buffer layer to 70 atomic percent in the topmost buffer layer.

[0200] In some embodiments, the substrate 10 includes one or more layers that at least have a metal, a metal alloy, and a metal-nitride / sulfide / oxide / silicide having the formula MX a , where M is a metal and X is nitrogen, sulfur, selenium, oxygen, silicon, and a is from about 0.4 to about 2.5. In some embodiments, the substrate 10 includes titanium, aluminum, cobalt, ruthenium, titanium nitride, tungsten nitride, tantalum nitride, and combinations thereof.

[0201] In some embodiments, the substrate 10 includes a dielectric material having at least the formula MX bsilicon, metal oxide, or nitride, where M is a metal or Si, X is nitrogen or oxygen, 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.

[0202] As ​ shown, in some embodiments, photoresist structure 22 is a three-layer photoresist structure, including bottom layer 20a, intermediate layer 20b, and upper photoresist layer 15. The upper layer of the three-layer photoresist structure 22 is a photosensitive layer or photoresist layer 15.

[0203] In some embodiments, bottom layer 20a is an organic material with a substantially flat upper surface, and intermediate layer 20b is an anti-reflection layer. In some embodiments, the organic material of bottom layer 20a includes a plurality of monomers or non-crosslinked polymers. In some embodiments, bottom layer 20a includes a material that can be patterned and / or has an adjustable composition to provide anti-reflection properties. Exemplary materials for bottom layer 20a include carbon chain polymers. Bottom layer 20a is used to planarize the structure because the structure beneath it may be uneven and depends on the device structure of the device layer beneath it. In some embodiments, bottom layer 20a is formed by a spin coating process. In certain embodiments, the thickness of bottom layer 20a ranges from about 3 nanometers to about 500 nanometers.

[0204] The intermediate layer 20b of the three-layer photoresist structure 22 may have a composition that provides anti-reflection properties for lithography operations and / or hard mask properties. In some embodiments, intermediate layer 20b includes a silicon-containing layer (such as a silicon hard mask material). Intermediate layer 20b may include a silicon-containing inorganic polymer. In other embodiments, intermediate layer 20b includes a silicone polymer. In other embodiments, intermediate layer 20b includes silicon oxide (such as spin-on glass (SOG)), silicon nitride, silicon oxynitride, polysilicon, a metal-containing organic polymer material containing metals such as titanium, titanium nitride, aluminum, and / or tantalum, and / or other suitable materials. Intermediate layer 20b can be bonded to adjacent layers, for example, by covalent bonds, hydrogen bonds, or hydrophilic-to-hydrophilic interactions. In some embodiments, based on the total weight of intermediate layer 20b, intermediate layer 20b includes additives at a concentration ranging from about 0.001 wt% to about 30 wt%. Below the disclosed concentration range of the additives, the additives may not be significant. Above the disclosed concentration range, the expected effects may not be significantly improved, or the beneficial properties of the intermediate layer may exhibit unacceptable degradation. In some embodiments, the thickness of intermediate layer 20b ranges from about 10 nanometers to about 200 nanometers.

[0205] In some embodiments, the composition included in the bottom layer 20 or the top layer 25 includes an adhesive, such as hexamethyldisilazane (HMDS), polymethylmethacrylate (PMMA), polyhydroxystyrene (PHS), or spin-on carbon (SOC); includes additives; and includes a solvent. In some embodiments, the bottom layer 20 or the top layer 25 is formed by spin coating. In some embodiments, the thickness of the bottom layer 20 is from about 10 nanometers to about 200 nanometers. In some embodiments, the thickness of the top layer 25 is from about 3 nanometers to about 100 nanometers. Bottom and top layer thicknesses below this range may not significantly improve the desired properties. Bottom layer thicknesses above this range may not provide any additional benefits. Top layer thicknesses above this disclosure range may interfere with the lithography pattern of the photoresist.

[0206] In some embodiments, the solvent of the bottom layer or top layer composition is selected from one or more of the group consisting of propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, 4-methyl-2-pentanol, acetone, methyl ethyl ketone, dimethylformamide (DMF), isopropanol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (MIBC), n-butyl acetate (nBA), 2-heptanone (MAK), and dioxane.

[0207] In some embodiments, the additives that inhibit or prevent free radical degradation of the photoresist include one or more radical inhibitors, thermal radical inhibitors, and photo radical inhibitors.

[0208] In some embodiments, the radical inhibitor is selected from one or more of the group consisting of phenothiazine, 2-tert-butyl-1,4-benzoquinone, 1,4-benzoquinone, hydroquinone, 4-tert-butylcatechol, 2,6-di-tert-butylphenol, 4-methoxyphenol, p-phenylenediamine, hydroxylamine, diethylhydroxylamine, 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl, 1,1-diphenyl-2-trinitrophenylhydrazyl radical, copper(II) dibutyldithiocarbamate, 6-tert-butyl-2,4-xylenol, 2,6-di-tert-butyl-p-cresol, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-TEMPO, 97%), 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl, 2,6-di-tert-butyl-4-methylphenol (2,6-di-tert-butyl-4-methylphenol, BHT, 99%), tert-butyl hydroquinone (tert-butyl hydroquinone, TBHQ, 97%), 2,6-di-tert-butyl-4-methoxyphenol (2,6-di-tert-butyl-4-methoxyphenol, DTBMP, 98%), and 4-methoxyphenol. Examples of the radical inhibitor according to the disclosed embodiments are shown in ​ .

[0209] In some embodiments, the thermal radical inhibitor is selected from one or more of the group consisting of azobisisobutyronitrile (AIBN), 2,2'-azodi(2-methylbutyronitrile) (AMBN), 2,2'-azobis(2,4-dimethyl)valeronitrile (ADVN), 4,4'-azobis(4-cyanopentanoic acid) (ACVA), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH), 2,2'-azobis[2-(2-imidazolin-2-yl))-propane] dihydrochloride, tert-butyl-hydroperoxide (TBHP), cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide (BPO), dicyandiamide, cyclohexyl toluenesulfonate, methyl diphenyl sulfonium tetrafluoroborate, benzyl(4-hydroxyphenyl)-methylsulfonium hexafluoroantimonate, and (4-hydroxyphenyl)methyl-(2-methylbenzyl) sulfonium hexafluoroantimonate. According to the disclosed embodiments, examples of the thermal radical inhibitor are shown in ​ .

[0210] In some embodiments, the photo radical inhibitor is selected from one or more of the group consisting of camphorquinone, acetophenone, 3-acetylphenol, 4-acetylphenol, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 3-hydroxybenzophenone, 3,4-dimethylbenzophenone, 4-hydroxybenzophenone, 4-benzoylbenzoic acid, 2-benzoylbenzoic acid, methyl 2-benzoylbenzoate, 4,4'-dihydroxybenzophenone, 4-(dimethylamino)-benzophenone, 4,4'-bis(dimethylamino)-benzophenone, 4,4'-bis(diethylamino)-benzophenone, 4,4'-dichlorobenzophenone, 4-(p-tolylthio)benzophenone, 4-phenylbenzophenone, 1,4-dibenzoylbenzene, benzyl, 4,4'-dimethylbenzyl, p-anisoyl, 2-benzoyl-2-propanol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 1-benzoylcyclohexanol, benzoin, and anisoin. According to the disclosed embodiments, examples of the photo radical inhibitor are shown in ​ and ​ .

[0211] In some embodiments, the concentration of the additive is from about 0.001 wt% to about 30 wt% based on the total weight of the bottom layer 20 or the top layer 25. Below the disclosed range of additive concentration, the photoresist properties may not be significantly improved. Above the disclosed range of additive concentration, there may be no additional significant improvement in the photoresist properties and it may have a detrimental effect on the photoresist properties.

[0212] The photoresist layer 15 is a photosensitive layer patterned by exposure to actinic radiation. Generally, the chemical properties of the incident radiation-exposed photoresist regions are changed depending on the type of photoresist used. The photoresist layer 15 is either a positive photoresist or a negative photoresist. A positive photoresist is a photoresist material that becomes soluble in a developer when exposed to, for example, ultraviolet radiation, while the regions of the photoresist material that are not exposed (or less exposed) are insoluble in the developer. On the other hand, a negative photoresist is a photoresist material that becomes insoluble in a developer when exposed to radiation, while the unexposed (or less exposed) photoresist regions are soluble in the developer. The regions of the negative photoresist that become insoluble upon exposure to radiation may become insoluble due to a crosslinking reaction caused by exposure to radiation.

[0213] In some embodiments, the photoresist layer comprises a highly sensitive photoresist composition. In some embodiments, the highly sensitive photoresist composition comprises a metal that has a high absorption of extreme ultraviolet (EUV) radiation.

[0214] In some embodiments, the photoresist layer 15 is made of a photoresist composition comprising a combination of a first compound or a first precursor and a second compound or a second precursor in the vapor state. The first precursor or the first compound is an organometal and has the formula as ​ shown: M a R b X c, where M is at least one of tin, bismuth, antimony, indium, tellurium, titanium, zirconium, hafnium, vanadium, cobalt, molybdenum, tungsten, aluminum, gallium, silicon, germanium, phosphorus, arsenic, yttrium, lanthanum, cerium or lutetium; R is a substituted or unsubstituted alkyl, alkenyl or carboxylate group. In some embodiments, M is selected from the group consisting of tin, bismuth, antimony, indium, tellurium and combinations thereof. In some embodiments, R is a C3-C6 alkyl, alkenyl or carboxylate. In some embodiments, R is selected from the group consisting of propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, secondary pentyl, tertiary pentyl, hexyl, isohexyl, secondary hexyl, tertiary hexyl and combinations thereof. X is a ligand, ion or other functional group capable of reacting with a second compound or second precursor; and in some embodiments, 1≤a≤2, b≥1, c≥1 and b + c≤5. In some embodiments, the alkyl, alkenyl or carboxylate group is substituted with one or more fluorine groups. In some embodiments, the organometallic precursor is a dimer, such as ​ as shown, where each monomer unit is connected to an amine group. Each monomer has the formula as defined above: M a R b X c .

[0215] In some embodiments, R is an alkyl group, such as C n H 2n+1 , where n≥3. In some embodiments, R is fluorinated, such as having the formula C n F x H ((2n+1)-x) . In some embodiments, R has at least one β-hydrogen or β-fluorine. In some embodiments, R is selected from the group consisting of isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl and sec-pentyl and combinations thereof.

[0216] In some embodiments, X is any functional group that is easily replaced by a second compound or second precursor to produce an M-OH functional group, such as selected from the group consisting of amines, including dialkylamino and monoalkylamino; alkoxy; carboxylate; halogen and sulfonic acid group. In some embodiments, the sulfonic acid group is substituted with one or more amine groups. In some embodiments, the halide is one or more selected from the group consisting of fluorine, chlorine, bromine and iodine. In some embodiments, the sulfonic acid group includes a substituted or unsubstituted C1-C3 group.

[0217] In some embodiments, the first organometallic compound or first organometallic precursor includes a metal core M + and a ligand L on the metal core M + , as ​ shown. In some embodiments, the metal core M +is a metal oxide. In some embodiments, the ligand L comprises a C3-C12 aliphatic or aromatic group. The aliphatic or aromatic group may be unbranched or branched, with cyclic or non-cyclic side chain groups containing 1-9 carbon atoms, including alkyl, alkenyl and phenyl groups. The branched groups may be further substituted with oxygen or halogen. In some embodiments, the C3-C12 aliphatic or aromatic group comprises a heterocyclic group. In some embodiments, the C3-C12 aliphatic or aromatic group is bonded to the metal through an ether or ester bond. In some embodiments, the aliphatic or aromatic group comprises a nitrite and a sulfonate substituent.

[0218] In some embodiments, the organometallic precursor or organometallic compound includes 2-hexyltris(dimethylamino)tin, 3-hexyltris(dimethylamino)tin, isohexyltris(dimethylamino)tin, n-hexyltris(dimethylamino)tin, 2-pentyltris(dimethylamino)tin, 3-pentyltris(dimethylamino)tin, isopentyltris(dimethylamino)tin, n-pentyltris(dimethylamino)tin, 2-butyltris(dimethylamino)tin, 3-butyltris(dimethylamino)tin, isobutyltris(dimethylamino)tin, n-butyltris(dimethylamino)tin, isopropyltris(dimethylamino)tin, n-propyltris(diethylamino)tin, and Compounds similar to alkyl (tri)(tert-oxy)tin include sec-hexyltri(tert-butoxy)tin, tert-hexyltri(tert-butoxy)tin, isohexyltri(tert-butoxy)tin, n-hexyltri(tert-butoxy)tin, sec-pentyltri(tert-butoxy)tin, 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(tri)dimethylaminotin, or n-propyltri(butoxy)tin. In some embodiments, the organometallic precursor or organometallic compound is fluorinated. In some embodiments, the boiling point of the organometallic precursor or compound is less than 200 degrees Celsius.

[0219] In some embodiments, the first compound or the first precursor includes one or more unsaturated bonds, which can coordinate with functional groups on the surface of the substrate between the bottom layer, such as hydroxyl groups, to improve the adhesion between the photoresist layer and the substrate or the bottom layer.

[0220] In some embodiments, the second precursor or second compound is at least one of an amine, a borane, a phosphine, or water. In some embodiments, the amine has the formula N p H n X m , wherein 0≤n≤3, 0≤m≤3, when p is 1 n+m=3, and when p is 2 n+m=4, each X is independently selected from the group consisting of fluorine, chlorine, bromine, and iodine. In some embodiments, the borane has the formula B p H n X m, where 0 ≤ n ≤ 3, 0 ≤ m ≤ 3, n + m = 3 when p is 1, and n + m = 4 when p is 2, and each X is independently selected from the group consisting of fluorine, chlorine, bromine, and iodine. In some embodiments, the phosphine has the formula P p H n X m , where 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 selected from the group consisting of fluorine, chlorine, bromine, and iodine.

[0221] In some embodiments, the second precursor or compound is water, ammonia water, or hydrazine. The reaction product of water, ammonia water, or hydrazine with the organometallic precursor or compound can form hydrogen bonds to increase the boiling point of the reaction product, prevent the release of the metal photoresist material, and thus prevent metal contamination. Hydrogen bonds also help prevent moisture from affecting the quality of the photoresist layer.

[0222] ​ Describe the reaction that occurs when the metal precursor is exposed to actinic radiation in some embodiments. Due to exposure to actinic radiation, the ligand L is released from the metal core M of the metal precursor, causing the cores of two or more metal precursors to bond to each other. + releases, causing the nuclei of two or more metal precursors to bond to each other.

[0223] ​ Illustrate examples of organometallic precursors according to the disclosed embodiments. In ​ , Bz is phenyl.

[0224] In some embodiments, operations S130, S220, S320, S420, and S520 perform a photoresist coating on a substrate or an underlying layer 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), while 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).

[0225] According to some embodiments disclosed, ​ describe a deposition apparatus 200 for a photoresist layer. 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 / flush gas supply 225 are connected to an inlet 230 in the chamber through a gas line 235, and a second precursor or compound gas supply 240 and the carrier / flush gas supply 225 are connected to another inlet 230' in the chamber through another gas line 235'. A vacuum pump 245 evacuates the chamber through an outlet 250 and an exhaust line 255 and removes excess reactants and reaction by-products. In some implementations, the flow rate or pulse of the precursor gas and the carrier / flush gas, the removal of excess reactants and reaction by-products, the pressure inside the vacuum chamber 205, and the temperature of the vacuum chamber 205 or the substrate support table 210 are controlled by a controller 260 configured to control each parameter.

[0226] In some embodiments, depositing a photoresist layer includes combining a first compound or first precursor with a second compound or second precursor in a vapor state to form a photoresist composition. In some embodiments, the first compound or first precursor and the second compound or second precursor of the photoresist composition are simultaneously introduced into a deposition vacuum chamber 205 (CVD chamber) through inlets 230 and 230'. In some embodiments, the first compound or first precursor and the second compound or second precursor are introduced into the deposition vacuum chamber 205 (ALD chamber) in an alternating manner through inlets 230 and 230', that is, first the first compound or precursor, then the second compound or precursor, and then the introduction of the first compound or precursor and the second compound or precursor is alternately repeated.

[0227] In some embodiments, the temperature of the deposition chamber ranges from about 30 degrees Celsius to about 400 degrees Celsius during the deposition operation, and in other embodiments, it ranges from about 50 degrees Celsius to about 250 degrees Celsius. In some embodiments, the pressure in the deposition chamber ranges from about 5 mTorr to about 100 Torr during the deposition operation, and in other embodiments, it ranges from about 100 mTorr to about 10 Torr. In some embodiments, the plasma power is less than about 1000 W. In some embodiments, the plasma power ranges from about 100 W to about 900 W. In some embodiments, the flow rates of the first compound or precursor and the second compound or precursor are from about 100 sccm to about 1000 sccm. In some embodiments, the flow ratio of the organometallic compound precursor to the second compound or precursor is from about 1:1 to about 1:5. Operating parameters outside the above ranges will result in an unsatisfactory photoresist layer in some embodiments. In some embodiments, the formation of the photoresist layer occurs in a single chamber (single-pot layer formation).

[0228] According to some disclosed embodiments, in a CVD process, the gas flows of two or more organometallic precursors and a second precursor are introduced into the deposition vacuum chamber 205 of a CVD apparatus through separate inlets 230 and the inlet path of gas line 235 and inlets 230' and the inlet path of gas line 235' so that they are mixed and react in the gas phase to form reaction products. In some embodiments, the gas flows are introduced using separate injection inlets 230 and 230' or a dual-pressure nozzle. The deposition apparatus is configured to mix the gas flows of the organometallic precursor and the second precursor in the chamber, prompting the organometallic precursor and the second precursor to react to form reaction products. Without limiting the disclosed mechanisms, functions, or utilities, the products of the vapor-phase reaction are believed to become heavier in molecular weight and then deposit onto the substrate 10 by condensation or other means.

[0229] In some embodiments, an ALD process is used to deposit a photoresist layer. During ALD, the surface of the substrate is exposed to alternating gaseous compounds (or precursors) to grow a layer on the substrate 10. Compared with CVD, the introduction of precursors is in continuous and non-overlapping pulses. In each pulse, the precursor molecules react with the surface in a self-limiting manner, causing the reaction to terminate 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 will depend on the nature of the interaction between the precursor and the surface.

[0230] In an embodiment of the ALD process, a pulsed organometallic precursor delivers a metal-containing precursor to the surface of the substrate 10 in the first half of the reaction. In some embodiments, the organometallic precursor reacts with a suitable underlying substance (such as a hydroxyl or amine functional group on the substrate surface) to form a new self-saturated surface. In some embodiments, excess unused reactants and reaction by-products are removed by evacuating with a vacuum pump 245 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. The ammonia 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 reaction substance to provide another self-limiting and saturated second half of the reaction. In some embodiments, a second purge is performed to remove unused reactants and reaction by-products. The pulses of the first precursor and the second precursor are alternated with the intervening purge operations until the desired photoresist layer thickness is reached.

[0231] In some embodiments, the photoresist layer 15 is formed with a thickness in the range of about 5 nanometers to about 50 nanometers, and in other embodiments, the thickness is in the range of about 10 nanometers to about 30 nanometers. One of ordinary skill in the art should recognize that additional thickness ranges within the above-specified ranges are contemplated and encompassed by the presently disclosed scope. The thickness can be evaluated using non-contact X-ray reflectometry and / or ellipsometry techniques based on the optical properties of the photoresist layer. In some embodiments, each photoresist layer has a fairly uniform thickness to facilitate the process. In some embodiments, the thickness variation of the deposited photoresist layer does not exceed ±25% of the average thickness, and in other embodiments, the thickness variation of each photoresist layer does not exceed ±10% of the average photoresist layer thickness. In some embodiments, for example, for high-uniformity deposition on a larger substrate, the edge exclusion of 1 cm can be used to evaluate the uniformity of the photoresist layer, that is, the uniformity of the layer is not evaluated for the coating portion within 1 cm of the edge. One of ordinary skill in the art should recognize that other ranges within the above-specified ranges are also contemplated and encompassed by the presently disclosed scope.

[0232] In some embodiments, the first and second compounds or precursors are delivered to the deposition vacuum chamber 205 by a carrier gas. The carrier gas, purge gas, deposition gas, or other process gases may include nitrogen, hydrogen, argon, neon, helium, or a combination thereof.

[0233] In some embodiments, the organometallic compound includes tin (Sn), antimony (Sb), bismuth (Bi), indium (In), and / or tellurium (Te) as metal components, but the disclosure is not limited to these metals. In other embodiments, additional suitable metals include titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), cobalt (Co), molybdenum (Mo), tungsten (W), aluminum (Al), gallium (Ga), silicon (Si), germanium (Ge), phosphorus (P), arsenic (As), yttrium (Y), lanthanum (La), cerium (Ce), lutetium (Lu), or a combination thereof. These additional metals can be used as substitutes for or added in addition to tin (Sn), antimony (Sb), bismuth (Bi), indium (In), and / or tellurium (Te).

[0234] The specific metal used can significantly affect the absorption of radiation. Therefore, the metal element can be selected according to the desired radiation and absorption cross-section. Tin, antimony, bismuth, tellurium, and indium have strong absorption in extreme ultraviolet light at 13.5 nanometers. Hafnium has good absorption of electron beam and extreme ultraviolet radiation. Metal components containing titanium, vanadium, molybdenum, or tungsten have strong absorption at longer wavelengths, for example, sensitivity to ultraviolet light wavelengths of 248 nanometers.

[0235] ​ The reactions that occur when the photoresist composition is exposed to actinic radiation and heated are described according to the disclosed embodiments. ​ Examples of the chemical structure of the photoresist layer in the photoresist patterning method at different stages are described according to the disclosed embodiments. As ​ shown, the photoresist composition includes an organometallic compound, such as SnX2R2, and a second compound, such as ammonia (NH3). When the organometallic compound and ammonia combine, the organometallic compound reacts with some ammonia in the vapor phase to form a reaction product in which the metal (tin) in the organometallic compound is bonded to an amine group. The amine groups in the deposited photoresist layer have hydrogen bonds, which can substantially increase the boiling point of the deposited photoresist layer to prevent the outgassing of the metal-containing photoresist material, thereby preventing the metal in the metal-containing photoresist from contaminating the deposition chamber and the process equipment of the semiconductor device. In addition, the hydrogen bonds of the amine groups can control the influence of moisture on the quality of the photoresist layer.

[0236] In some embodiments, the photoresist composition is an organic polymer-based composition and is deposited by a spin coating process in a solvent, and then the solvent is removed by a first heating.

[0237] When subsequently exposed to extreme ultraviolet radiation, the organometallic compound absorbs the extreme ultraviolet radiation and one or more organic R groups are cleaved from the organometallic compound to form an amino-metal compound in the radiation exposure region. Subsequently, when performing the post-exposure bake (PEB) operations S160, S280, S370, S450, and S550, the amino-metal compound crosslinks through the amine groups in some embodiments, as ​ shown. In some embodiments, partial crosslinking of the amino-metal compound is due to exposure to extreme ultraviolet radiation.

[0238] ​ According to the disclosed embodiments, a continuous process stage of an operation is described. An additive is introduced into the photoresist layer 15 to inhibit or prevent free radical degradation of the photoresist. The bottom layer 20 including the additive is formed on the substrate 10, as ​ shown. The bottom layer composition can be any composition disclosed herein, and the method of forming the bottom layer 20 can be any suitable method disclosed herein. Subsequently, the photoresist layer 15 is formed on the bottom layer 20, as ​ shown. The composition of the photoresist layer can be any composition disclosed herein, and the method of forming the photoresist layer 15 can be any suitable method disclosed herein. The photoresist layer 15 and the bottom layer 20 are then heated or baked using a heater 21, as ​ shown. In some embodiments, the heater 21 is a resistive heating element, an infrared heating element, or a hot plate. In some embodiments, the heating or baking operations (operations S140, S260, S370, and S450) include heating the photoresist layer 15 and the bottom layer 20 at a temperature between about 40 degrees Celsius and about 250 degrees Celsius for about 10 seconds to about 10 minutes. The heating or baking operations cause the additive to diffuse from the bottom layer 20 into the photoresist layer 15. In some embodiments, the additive diffuses throughout the photoresist layer 15. In some embodiments, the additive diffuses uniformly throughout the photoresist layer 15. In other embodiments, the additive diffuses into the photoresist layer to form a concentration gradient and has the highest concentration at the interface of the photoresist layer 15 / bottom layer 20.

[0239] ​ According to the disclosed embodiments, a continuous process stage of an operation is described. An additive is introduced into the photoresist layer 15 to inhibit or prevent free radical degradation of the photoresist. The bottom layer 20' is formed on the substrate 10, as ​ shown. The bottom layer composition can be any composition disclosed herein and does not contain the additive, and the method of forming the bottom layer 20' can be any suitable method disclosed herein. The additive 19 is then added to the bottom layer 20', as ​As shown. Additive 19 is introduced into the underlying layer 20' by diffusing the additive from the additive-containing vapor into the underlying layer 20'. In some embodiments, the additive-containing vapor is generated by volatilizing the additive, ALD, CVD, PE-ALD, PE-CVD, MO-CVD, AP-CVD, or LP-CVD. In some embodiments, based on the total weight of the vapor, the concentration of additive 19 in the vapor is from about 0.001 wt% to about 100 wt%. In other embodiments, additive 19 is dissolved in a solvent, and this additive / solvent mixture is applied to the underlying layer 20', and then the solvent is removed by heating the underlying layer 20' at a temperature from about 60 degrees Celsius to about 300 degrees Celsius, thereby forming an underlying layer 20 containing the additive, as ​ shown. In some embodiments, the solvent is one or more organic or water / inorganic solvents. Organic solvents include: 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, acetone, dimethylformamide (DMF), isopropanol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (MIBC), n-butyl acetate (nBA), 2-heptanone (MAK), tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), and combinations thereof, etc. In some embodiments, the organic solvent is a low-polarity solvent, including straight-chain or branched alkanes, such as octane and 2-methylheptane; or ethers, including dipropyl ether and isoamyl ether. In some embodiments, the organic solvent is a liquid at room temperature and has a boiling point from about 60 degrees Celsius to about 280 degrees Celsius. In some embodiments, the water / inorganic solvent is one or more of water, potassium hydroxide, sodium hydroxide, hydrochloric acid, hydrofluoric acid, etc.

[0240] Then, a photoresist layer 15 is formed on the underlying layer 20, as ​As shown. The photoresist layer composition can be any composition disclosed herein, and the method of forming the photoresist layer 15 can be any suitable method disclosed herein. The photoresist layer 15 and the underlying layer 20 are then heated or baked using a heater 21, as ​ shown. In some embodiments, the heater 21 is a resistive heating element, an infrared heating element, or a hot plate. In some embodiments, the heating or baking operation (operation S140, operation S260, operation S370, and operation S450) includes heating the photoresist layer 15 and the underlying layer 20 at a temperature of about 40 degrees Celsius to about 250 degrees Celsius for about 10 seconds to about 10 minutes. The heating or baking operation causes the additive to diffuse from the underlying layer 20 into the photoresist layer 15. In some embodiments, the additive diffuses throughout the photoresist layer 15. In some embodiments, the additive diffuses uniformly throughout the photoresist layer 15. In other embodiments, the additive diffuses into the photoresist layer to form a concentration gradient and has the highest concentration at the interface of the photoresist layer 15 / underlying layer 20.

[0241] ​ The sequential process stages of the operation are illustrated according to the disclosed embodiments. An additive is introduced into the photoresist layer 15 to inhibit or prevent free radical degradation of the photoresist. The photoresist layer 15 is formed on the substrate 10, as ​ shown. The photoresist layer composition can be any composition disclosed herein, and the method of forming the photoresist layer 15 can be any suitable method disclosed herein. A top layer 25 including the additive is formed on the photoresist layer 15, as ​ shown. The top layer composition can be any composition disclosed herein, and the method of forming the top layer 25 can be any suitable method disclosed herein. The photoresist layer 15 and the top layer 25 are then heated or baked using a heater 21, as ​ shown. In some embodiments, the heater 21 is a resistive heating element, an infrared heating element, or a hot plate. In some embodiments, the heating or baking operation (operation S140, operation S260, operation S370, and operation S450) includes heating the photoresist layer 15 and the top layer 25 at a temperature of about 40 degrees Celsius to about 250 degrees Celsius for about 10 seconds to about 10 minutes. The heating or baking operation causes the additive to diffuse from the top layer 25 into the photoresist layer 15. In some embodiments, the additive diffuses throughout the photoresist layer 15. In some embodiments, the additive diffuses uniformly throughout the photoresist layer 15. In other embodiments, the additive diffuses into the photoresist layer to form a concentration gradient and has the highest concentration at the interface of the photoresist layer 15 / top layer 25.

[0242] ​ The sequential process stages of the operation are illustrated according to the disclosed embodiments. An additive is introduced into the photoresist layer 15 to inhibit or prevent free radical degradation of the photoresist. The photoresist layer 15 is formed on the substrate 10, as​ The photoresist layer composition can be any composition disclosed herein, and the method for forming the photoresist layer 15 can be any suitable method disclosed herein. The top layer 25' is then formed on the photoresist layer of the substrate, such as ​ The top layer composition can be any composition disclosed herein and does not contain additives, and the method of forming the top layer 25' can be any suitable method disclosed herein. The additive 19 is then added to the top layer 25', such as ​ Additive 19 is incorporated herein by reference. ​ Any of the disclosed techniques are introduced into the top layer 25' to form the top layer 25 with the additive. The photoresist layer 15 and the top layer 25 are then heated or baked using a heater 21, such as ​ As shown. In some embodiments, the heater 21 is a resistive heating element, an infrared heating element, or a hot plate. In some embodiments, the heating or baking operations (operation S140, operation S260, operation S370, and operation S450) include heating the photoresist layer 15 and the top layer 25 at a temperature between about 40 degrees Celsius and about 250 degrees Celsius for about 10 seconds to about 10 minutes. The heating or baking operations cause the additive to diffuse from the top layer 25 into the photoresist layer 15. In some embodiments, the additive diffuses throughout the photoresist layer 15. In some embodiments, the additive diffuses uniformly throughout the photoresist layer 15. In other embodiments, the additive diffuses into the photoresist layer to form a concentration gradient, with the highest concentration at the photoresist layer 15 / top layer 25 interface.

[0243] ​ According to the disclosed embodiment, an additive is introduced into the photoresist layer 15 to inhibit or prevent free radicals from degrading the photoresist. The photoresist layer 15 is formed on the substrate 10, such as ​ The photoresist layer composition can be any composition disclosed herein, and the method for forming the photoresist layer 15 can be any suitable method disclosed herein. ​ Any of the disclosed techniques are directly introduced into the photoresist layer 15, such as ​ The photoresist layer 15 is then heated or baked using a heater 21, as shown. ​ As shown. In some embodiments, heater 21 is a resistive heating element, an infrared heating element, or a hot plate. In some embodiments, the heating or baking operation includes heating the photoresist layer 15 at a temperature of approximately 40 degrees Celsius to approximately 250 degrees Celsius for approximately 10 seconds to approximately 10 minutes. The heating or baking operation causes the additive to diffuse throughout the photoresist layer 15. In some embodiments, the additive diffuses uniformly throughout the photoresist layer 15. In other embodiments, the additive diffuses into the photoresist layer to form a concentration gradient from the top to the bottom of the photoresist layer. ​It is noted that two or more embodiments may be combined and detailed descriptions thereof may be omitted.

[0244] ​ According to different disclosed embodiments, an operation of selectively or patternwise exposing a photoresist layer 15 is described (see operations S150, S270, S340, S440, and S540 in ​ ). ​ According to the disclosed embodiments, actinic radiation 45 passes through a photomask 30 to expose the photoresist layer 15 over the underlying layer 20 to the actinic radiation 45, so as to form an exposed portion 50 and an unexposed portion of the photoresist layer 15. ​ According to the disclosed embodiments, actinic radiation 45 passes through a photomask 30 to expose the photoresist layer 15 having a top layer 25 to the actinic radiation 45, so as to form an exposed portion 50 and an unexposed portion 52 of the photoresist layer 15. ​ According to the disclosed embodiments, actinic radiation 45 passes through a photomask 30 to expose the photoresist layer 15 to the actinic radiation 45, so as to form an exposed portion 50 and an unexposed portion 52 of the photoresist layer 15. ​ According to the disclosed embodiments, extreme ultraviolet radiation 97 reflected by a reflective photomask 65 exposes the photoresist layer 15 over the underlying layer 20 to the extreme ultraviolet radiation 97, so as to form an exposed portion 50 and an unexposed portion of the photoresist layer 15. ​ According to the disclosed embodiments, extreme ultraviolet radiation 97 reflected by a reflective photomask 65 exposes the photoresist layer 15 having a top layer 25 to the extreme ultraviolet radiation 97, so as to form an exposed portion 50 and an unexposed portion 52 of the photoresist layer 15. ​ According to the disclosed embodiments, extreme ultraviolet radiation 97 reflected by a reflective photomask 65 exposes the photoresist layer 15 to the extreme ultraviolet radiation 97, so as to form an exposed portion 50 and an unexposed portion 52 of the photoresist layer 15.

[0245] In some other embodiments, a top layer 25 having additives to inhibit or prevent free radical degradation of the photoresist is formed on the selectively or patternwise exposed photoresist layer 15, as shown in ​ and ​ (see operation S460 in ​ ). The top layer 25 is formed by any suitable composition and any suitable method disclosed herein. In some embodiments, a top layer 25' without additives is formed on the selectively or patternwise exposed photoresist layer, as shown in ​ and ​ (see operation S350 in ​ ). Additives 19 that inhibit or prevent free radical degradation of the photoresist are then introduced into the top layer 25', as shown in ​ (see​ in operation S360), to form the top layer 25, as ​ shown. The top layer 25' without additives is formed by any suitable composition and any appropriate method disclosed herein. The additive 19 is introduced into the top layer 25' by any suitable method disclosed herein.

[0246] In some embodiments, the additive 19 that inhibits or prevents photoresist degradation by free radicals is introduced directly into the photoresist layer 15 after the photoresist layer is selectively or patternwise exposed, as ​ and ​ shown. The additive 19 is introduced into the selectively or patternwise exposed photoresist layer 15 by any technique of any reference ​ disclosed herein.

[0247] ​ The operations of developing the selectively or patternwise exposed photoresist layer 15 are described according to various disclosed embodiments (see ​ operations S170, operation S290, operation S380, operation S480, and operation S560 in ​ Describe developing a photoresist layer located above the bottom layer 20 and selectively or patternwise exposed to actinic radiation using a composition of a liquid developer 57 supplied from a dispenser 62. The developer composition and the developing operation can be any suitable developer and operation disclosed herein with reference to operation S170. ​ Describe developing a photoresist layer 15 having a top layer 25 located above and selectively or patternwise exposed to actinic radiation using a composition of a liquid developer 57 supplied from a dispenser 62. The developer composition and the developing operation can be any suitable developer and operation disclosed herein with reference to operation S170. ​ Describe developing a photoresist layer selectively or patternwise exposed to actinic radiation using a composition of a liquid developer 58 containing an additive supplied from a dispenser 62 to inhibit or prevent free radicals from reducing the photoresist. The composition of the developer 58 includes a solvent and an additive. The solvent can be any solvent disclosed herein with reference to operation S170, and the developing operation can be any operation disclosed herein with reference to operation S170. The additive can be any additive disclosed herein with reference to ​ disclosed.

[0248] ​ Describe dry developing of a photoresist layer 15 selectively or patternwise exposed above the bottom layer 20. ​ Describe dry developing of a photoresist layer 15 selectively or patternwise exposed having a top layer 25. ​Describe the dry development of a photoresist layer 15 with selective or patterned exposure, where additives are introduced directly into the photoresist layer and there is no underlying or overlying layer. The dry developer composition and the operation of dry development can be any suitable dry development composition or operation disclosed herein.

[0249] ​ Describe the patterning of a three - layer photoresist structure 22 according to some disclosed embodiments. In some embodiments, the underlying layer 20 of the three - layer photoresist structure 22 includes a bottom layer 20a and an intermediate layer 20b and is formed on a substrate 10. The bottom layer 20a and the intermediate layer 20b can be made of any material as seen herein ​ disclosed. The photoresist layer 15 is then formed on the underlying layer and is selectively exposed to form exposed portions 50 and unexposed portions 52 by the photoresist formation and exposure operations as seen herein ​ disclosed.

[0250] As ​ shown, the photoresist layer 15 is then developed by any developing operation disclosed herein to form a photoresist layer with an opening pattern 55 that exposes the intermediate layer 20b. In some embodiments, the photoresist layer 15 is a positive photoresist, as ​ shown. In other embodiments, the photoresist layer 15 is a negative photoresist. Then as ​ shown, the opening pattern 55 of the photoresist layer 15 is transferred to the intermediate layer 20b by an etching operation to expose the bottom layer 20a from the recessed pattern 55' of the intermediate layer. The photoresist layer is then removed by an appropriate photoresist stripping operation, and the recessed pattern 55' of the intermediate layer 20b is transferred to the bottom layer 20a by an appropriate etching operation to expose the substrate 10 from the pattern 55” of the bottom layer 20a, as ​ shown. The pattern 55” of the intermediate layer is then transferred to the substrate 10 by an appropriate etching operation to form a pattern 55”' on the substrate, and the intermediate layer 20b and the bottom layer 20a are removed by an appropriate etching operation, as ​ shown.

[0251] In some embodiments, the photoresist structure 22 includes an underlying layer 20' and an overlying layer 25, as ​ shown. In some embodiments, the underlying layer 20' includes a bottom layer 20a and an intermediate layer 20b. In some embodiments, the underlying layer 20' does not contain additives. In some embodiments including the underlying layer 20', the photoresist structure includes an overlying layer containing additives.

[0252] In other embodiments, both the underlying layer 20 and the overlying layer 25 contain additives, and when the photoresist structure is heated, the additives diffuse from the underlying layer 20 and the overlying layer 25 into the photoresist layer 15.

[0253] In some embodiments, before forming the photoresist layer 15, the layer to be patterned or target layer 60 is placed on a substrate, as ​ shown. In some embodiments, the target layer is a metal layer or a dielectric layer disposed on a metal layer, such as a passivation layer. In embodiments where the target layer 60 is a metal layer, the target layer 60 is formed of a conductive material by using a metallization process and metal deposition techniques including chemical vapor deposition, atomic layer deposition, and physical vapor deposition (sputtering). Similarly, if the target layer 60 is a dielectric layer, the target layer 60 is formed by dielectric layer formation techniques including thermal oxidation, chemical vapor deposition, atomic layer deposition, and physical vapor deposition.

[0254] As ​ shown, in some embodiments, a top layer 25 containing additives to inhibit or prevent free radical degradation of the photoresist is formed on the photoresist layer. The top layer 25 and the method of forming the top layer 25 can be any suitable top layer composition and forming method disclosed herein. In some embodiments, a bottom layer 20 containing additives is formed on the target layer before forming the photoresist layer according to any suitable bottom layer forming method disclosed herein.

[0255] ​ and ​ illustrate embodiments of selectively exposing the top layer 25 and the photoresist layer 15 to actinic radiation 45 / extreme ultraviolet radiation 97. The exposure disclosed herein can be any of the exposure operations referring to operation S150, operation S270, operation S340, operation S440, and operation S540.

[0256] As ​ and ​ shown. The photoresist layer is then developed by any developing operation disclosed herein to form a photoresist layer having an opening pattern 55 that exposes the target layer 60. Refer to operation S170, operation S290, operation S380, operation S480, and operation S560 herein to form an opening pattern of the photoresist to expose the target layer 60, as ​ shown. ​ illustrates a liquid developing operation, ​ illustrates a dry developing operation. As ​ shown, in some embodiments, the photoresist is a negative photoresist, where the exposed portion 50 of the photoresist remains after development. In other embodiments, the photoresist is a positive photoresist.

[0257] Next, as ​ shown, the opening pattern 55 of the photoresist layer 15 is transferred to the target layer 60 by an etching operation, and the photoresist layer is removed to form a recessed pattern 55' in the target layer.

[0258] The disclosed embodiments include a photoresist structure, the photoresist structure including: a bottom layer containing an additive; a double-layer bottom layer including a bottom layer and an intermediate layer, wherein the intermediate layer contains an additive; a top layer containing an additive; a bottom layer and a top layer containing an additive; a bottom layer without an additive and a top layer containing an additive; a double-layer bottom layer without an additive and a top layer containing an additive; and no bottom layer and top layer.

[0259] Other embodiments include other operations before, between, 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. In these embodiments, further included are etching the substrate through the 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 the STI features to form fin-shaped active regions. In some embodiments, one or more gate electrodes are formed on the substrate. Some embodiments include forming gate spacers, doping source / drain regions, contacts for gate / source / drain features, etc. In other embodiments, a target pattern is formed with metal lines in a multi-layer interconnect structure. For example, the metal lines can be formed in an inter-layer dielectric (ILD) layer of the substrate and etched to form a plurality of trenches. The trenches may be filled with a conductive material, such as metal; and the conductive material can be polished through processes such as chemical mechanical planarization (CMP) to expose the patterned ILD layer, thereby forming the metal lines in the ILD layer. The above are non-limiting examples of devices / structures that can be fabricated and / or improved using this method.

[0260] In some embodiments, the active elements are formed according to the disclosed embodiments, 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) field-effect transistors, other memories, and combinations thereof, etc.

[0261] According to the disclosed embodiments, a novel treatment of the photoresist layer with an additive is performed to inhibit or prevent the degradation of the photoresist layer by radicals such as hydrogen radicals. The semiconductor devices provided according to the presently disclosed embodiments have high feature resolution and density at a higher wafer exposure throughput, reducing defects with a higher process efficiency compared to traditional exposure techniques. Compared with semiconductor manufacturing methods that do not use the method of treating the photoresist layer with an additive according to the present disclosure, the disclosed embodiments improve the line width roughness and the uniformity of critical dimensions by more than 3%. In addition, the disclosed embodiments reduce defects by more than 5% and allow the lithography exposure dose to be reduced by more than 3%. In some embodiments, a photoresist pattern with a pitch less than 40 nanometers can be formed according to the disclosed method. In some embodiments, the line width roughness of the photoresist pattern formed according to this disclosure is less than about 5.0 nanometers, and the exposure dose for forming such a pattern is less than about 70 mj.

[0262] The disclosed embodiments are a method of manufacturing a semiconductor device, comprising: forming a photoresist structure including forming a photoresist layer including a photoresist composition on a substrate; and after forming the photoresist layer, treating the photoresist layer with an additive, wherein the additive is one or more selected from the group consisting of a radical inhibitor, a thermal radical inhibitor, and a photo radical inhibitor. In some embodiments, the photoresist composition includes a metal. In some embodiments, the photoresist composition includes an organometallic compound. In some embodiments, forming the photoresist structure further includes forming an underlying layer including an underlying composition on the substrate before forming the photoresist layer, wherein the underlying composition includes the additive, and when treating the photoresist layer with the additive, the additive diffuses from the underlying layer to the photoresist layer. In some embodiments, forming the photoresist structure further includes forming a top layer including a top composition on the photoresist layer after forming the photoresist layer, wherein the top composition includes the additive, and when treating the photoresist layer with the additive, the additive diffuses from the top layer to the photoresist layer. In some embodiments, forming the photoresist structure includes forming a three-layer photoresist structure, comprising: forming a bottom layer on the substrate; forming an intermediate layer on the bottom layer; and forming an upper layer on the intermediate layer, wherein the upper layer is the photoresist layer. In some embodiments, the intermediate layer includes the additive, and when treating the photoresist layer with the additive, the additive diffuses from the intermediate layer to the photoresist layer. In some embodiments, forming the photoresist structure further includes forming a top layer on the upper layer, the top layer including the additive, and when treating the photoresist layer with the additive, the additive diffuses from the top layer to the photoresist layer. In some embodiments, the bottom layer includes an organic polymer, and the intermediate layer includes a silicon-containing compound. In some embodiments, the method further includes: selectively exposing the photoresist layer to actinic radiation; and after selectively exposing the photoresist layer to actinic radiation, applying a developer to the photoresist layer. In some embodiments, treating the photoresist layer with the additive includes applying a developer, and the developer includes the additive.

[0263] Another disclosed embodiment is a method of manufacturing a semiconductor device, comprising: forming a metal-containing photoresist layer on a substrate; forming a first layer on the substrate before forming the metal-containing photoresist layer or on the metal-containing photoresist layer after forming the metal-containing photoresist layer; and diffusing an additive from the first layer to the metal-containing photoresist layer, wherein the additive is one or more selected from the group consisting of a radical inhibitor, a thermal radical inhibitor, and a photo radical inhibitor. In some embodiments, diffusing the additive from the first layer to the metal-containing photoresist layer includes heating the first layer and the metal-containing photoresist layer. In some embodiments, the additive is added to the first layer by one or more selected from the group consisting of mixing the additive into the first layer composition before forming the first layer, treating the first layer with a solvent mixture including the additive, doping the first layer with the additive, diffusing the additive from a vapor including the additive to the first layer, or copolymerizing the first layer with the additive.

[0264] Another disclosed embodiment is a method of manufacturing a semiconductor device, comprising: forming a photoresist layer on a substrate, wherein the photoresist layer includes a metal photoresist composition; forming a top layer on the photoresist layer, wherein the top layer includes a polymer and a radical inhibiting compound; patternwise exposing the photoresist layer to actinic radiation; and developing the patternwise exposed photoresist layer to form a pattern in the photoresist layer. In some embodiments, the method further comprises forming a bottom layer on the substrate before forming the photoresist layer. In some embodiments, the top layer is formed on the photoresist layer by coating a top layer composition including a solvent and a radical inhibiting compound. In some embodiments, the top layer is formed on the photoresist layer by vapor deposition. In some embodiments, the method further comprises heating the top layer to diffuse the radical inhibiting compound from the top layer to the photoresist layer. In some embodiments, the radical inhibiting compound is one or more selected from the group consisting of a radical inhibitor, a thermal radical inhibitor, and a photo radical inhibitor.

[0265] The foregoing outlines the features of several embodiments or examples, enabling those of ordinary skill in the art to better understand various aspects of the present disclosure. Those of ordinary skill in the art should recognize that they can readily use the present disclosure as a basis for designing or modifying other processes and structures to achieve the same purposes and / or achieve the same advantages as the embodiments or examples described herein. Those of ordinary skill in the art should also recognize that such equivalent structures 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 of manufacturing a semiconductor device, characterized in that, Comprising: Forming a photoresist structure, including forming a photoresist layer comprising a photoresist composition on a substrate; Selectively exposing the photoresist layer to actinic radiation; After selectively exposing the photoresist layer to the actinic radiation, treating the photoresist layer with an additive, wherein treating the photoresist layer with the additive comprises: Forming a top layer comprising a top layer composition on the exposed and unexposed portions of the selectively exposed photoresist layer, wherein the top layer composition comprises the additive, and the additive is one or more radical inhibitors; and Heating the top layer to diffuse the additive from the top layer into the photoresist layer; and After treating the photoresist layer with the additive, developing the photoresist layer.

2. The method according to claim 1, characterized in that, The photoresist composition comprises a metal.

3. The method according to claim 1, wherein The photoresist composition comprises an organometallic compound.

4. The method according to claim 1, wherein Forming the photoresist structure further comprises forming a bottom layer comprising a bottom layer composition on the substrate before forming the photoresist layer, wherein the bottom layer composition comprises the additive, and the additive diffuses from the bottom layer into the photoresist layer.

5. The method according to claim 1, characterized in that, The additive is one or more selected from the group consisting of a thermal radical inhibitor and a photo radical inhibitor.

6. The method according to claim 1, characterized in that, Forming the photoresist structure comprises forming a three-layer photoresist structure, including: Forming a bottom layer on the substrate; Forming an intermediate layer on the bottom layer; and Forming an upper layer on the intermediate layer, wherein the upper layer is the photoresist layer.

7. The method according to claim 6, wherein The intermediate layer further comprises the additive, and the additive diffuses from the intermediate layer into the photoresist layer.

8. The method according to claim 6, characterized in that, The bottom layer comprises an organic polymer, and the intermediate layer comprises a silicon-containing compound.

9. The method according to claim 1, characterized in that Developing the photoresist layer comprises applying a developer to the photoresist layer.

10. The method according to claim 9, wherein The developer comprises the additive.

11. A method of manufacturing a semiconductor device, characterized in that, Comprising: Forming a metal-containing photoresist layer on a substrate; Selectively exposing the metal-containing photoresist layer to actinic radiation; After selectively exposing the metal-containing photoresist layer to the actinic radiation, forming a first layer on the exposed and unexposed portions of the metal-containing photoresist layer; Heating the first layer and the metal-containing photoresist layer to diffuse an additive from the first layer into the metal-containing photoresist layer, wherein the additive is one or more radical inhibitors; and After diffusing the additive, applying a developer to the selectively exposed metal-containing photoresist layer.

12. The method according to claim 11, wherein The additive is one or more selected from the group consisting of a thermal radical inhibitor and a photo radical inhibitor.

13. The method according to claim 11, wherein The additive is added to the first layer by one or more selected from the group consisting of mixing the additive into a first layer composition before forming the first layer, treating the first layer with a solvent mixture comprising the additive, doping the first layer with the additive, diffusing the additive from a vapor comprising the additive into the first layer, or copolymerizing the first layer with the additive.

14. A method of manufacturing a semiconductor device, characterized in that, Comprising: Forming a photoresist layer on a substrate, wherein the photoresist layer comprises a metal photoresist composition; Patternwise exposing the photoresist layer to actinic radiation; Forming a top layer on the exposed and unexposed portions of the patternwise exposed photoresist layer, wherein the top layer comprises a polymer and a radical inhibiting compound; Heat the top layer to diffuse the radical inhibitor compound from the top layer into the photoresist layer; and After forming the top layer, develop the patterned exposed photoresist layer to form a pattern in the photoresist layer.

15. The method according to claim 14, wherein Further includes forming a bottom layer on the substrate before forming the photoresist layer.

16. The method according to claim 14, wherein The top layer is formed on the photoresist layer by coating a top layer composition including a solvent, the polymer, and the radical inhibitor compound.

17. The method according to claim 14, wherein The top layer is formed on the photoresist layer by chemical vapor deposition.

18. The method according to claim 14, wherein The metal photoresist composition includes an organometallic compound.

19. The method according to claim 14, wherein The radical inhibitor compound is one or more selected from the group consisting of a thermal radical inhibitor and a photo radical inhibitor.

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