Improved method for forming an unexposed photoresist layer

Abstract

To provide a method of forming an enhanced unexposed photoresist layer from an unexposed photoresist layer on a substrate by increasing the sensitivity of the unexposed photoresist to exposure radiation.SOLUTION: The method comprises: providing the substrate with the unexposed photoresist layer in a reaction chamber; providing a first precursor comprising a portion of a photosensitizer reacting sensitively to exposure radiation in the reaction chamber; and infiltrating the unexposed photoresist layer on the substrate with the first precursor.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure generally relates to methods and systems for manufacturing electronic devices. More particularly, the present disclosure relates to a method of forming an improved unexposed photoresist layer. Background Art

[0002] As trends have driven semiconductor devices to smaller sizes, various patterning techniques have emerged. These techniques include immersion (ArF) lithography using 193 nm exposure radiation combined with double or quad patterning, extreme ultraviolet (EUV) lithography using exposure radiation around 13.5 nm, and EUV combined with double or quad patterning.

[0003] Patterning techniques can employ at least one photoresist disposed on a substrate to enable high-resolution patterning of the substrate by exposure radiation of a lithography system. To meet both the requirements of high resolution and low line edge roughness, the photoresist can be a thin layer.

[0004] However, photoresists have several drawbacks. In particular, high-resolution photoresists may have low sensitivity to radiation used in lithography processes. The sensitivity of an unexposed photoresist can be defined as the minimum energy in mJ / cm² that may be required to produce defined features in the photoresist on a substrate. Photoresist sensitivity is important when using deep ultraviolet (ArF) or extreme ultraviolet (EUV) exposure radiation. For example, in lithography, the radiation intensity generated by the tool may be low, so tool throughput can be low if a low-sensitivity photoresist is used.

[0005] Therefore, to improve the throughput of lithography tools, it may be advantageous to increase the sensitivity of unexposed photoresists to exposure radiation from lithography tools. [Overview of the project]

[0006] According to at least one embodiment of the present invention, A layer of unexposed photoresist is provided on the substrate inside the reaction chamber, The present invention provides a method for forming an improved unexposed photoresist layer on a substrate that is more sensitive to exposure radiation, by supplying a first precursor containing at least a portion of a photosensitizer that reacts sensitively to exposure radiation to a substrate in a reaction chamber, thereby allowing the first precursor to permeate the unexposed photoresist layer on the substrate for a first period T1. By permeating the unexposed photoresist layer on the substrate with a first precursor containing at least a portion of a photosensitizer that reacts sensitively to exposure radiation for a first period T1, the amount of photosensitizer in the unexposed photoresist layer can be increased. For example, since the photosensitizer is insoluble in photoresist, the amount of photosensitizer in the photoresist can be limited before rotating the photoresist on the substrate. By permeating at least a portion of the photosensitizer after rotating the unexposed photoresist layer on the substrate, an excess of photosensitizer can be supplied to the photoresist layer.

[0007] To summarize the invention and its advantages that go beyond the prior art, some objectives and advantages of the invention have been described above in this specification. Of course, not all such objectives or advantages are necessarily achieved according to every particular embodiment of the invention. It should be understood that this is also a good thing. Therefore, those skilled in the art will recognize that the present invention may be embodied or practiced in a manner that achieves or optimizes one advantage or a group of advantages, for example, as taught or suggested herein, without necessarily achieving other objectives or advantages, which may also be taught or suggested herein.

[0008] All of these embodiments are intended to be within the scope of the invention disclosed herein. To those skilled in the art, these and other embodiments will be readily apparent from the accompanying drawings, from the subsequent embodiments for carrying out the invention of a particular embodiment, and the invention is not limited to all specific embodiments disclosed. [Brief explanation of the drawing]

[0009] These and other features, aspects, and advantages of the invention disclosed herein are described below with reference to the drawings of some embodiments and are intended to be illustrative and not limiting to the invention.

[0010] [Figure 1] This is a flowchart according to at least one embodiment of the present invention.

[0011] [Figure 2] This disclosure illustrates exemplary systems based on various exemplary embodiments of this disclosure.

[0012] [Figure 3] Additional exemplary systems are shown by various exemplary embodiments of this disclosure.

[0013] It should be understood that the elements in the drawings are illustrative for the sake of brevity and clarity and are not necessarily drawn to scale. For example, some dimensions of the elements in the drawings may be emphasized more than others to help improve understanding of the embodiments shown in this disclosure. [Modes for carrying out the invention]

[0014] While certain embodiments and examples are disclosed below, it will be understood by those skilled in the art that the present invention extends beyond the embodiments and / or uses of the invention specifically disclosed, as well as their obvious variations and equivalents. Therefore, the scope of the invention disclosed is not intended to be limited by the embodiments described and specifically disclosed below.

[0015] Embodiments of the present invention relate to a combination of a hard mask film penetration process. This combination of an unexposed photoresist layer and a penetration process can significantly alter the properties of the unexposed photoresist layer (e.g., etching rate or even LER of the width of patterned features).

[0016] Figure 1 illustrates a method 100 according to at least one embodiment of the present invention. Method 100 includes a first step 110 of supplying a substrate into a reaction chamber, wherein the substrate has an unexposed photoresist layer. The unexposed photoresist layer can be provided on the substrate using a spin coater. The unexposed photoresist layer can be provided directly on the substrate or on one or more mask layers provided on the substrate surface. Mask layers may be provided to improve the etching resistance or adhesion of the photoresist, and / or the mask layers may function as an anti-reflective coating.

[0017] Method 100 may include a first step 120a in which an unexposed photoresist layer on a substrate can be impregnated with a penetrating material by supplying a first precursor containing at least a portion of a photosensitizer to the unexposed photoresist layer on the substrate in a reaction chamber. The photosensitizer may be sensitive to exposure radiation (e.g., EUV) used in a subsequent lithography system. The unexposed photoresist layer on the substrate can be impregnated with a first precursor that increases the sensitivity of the unexposed photoresist to exposure radiation for a first period T1.

[0018] The supply and infiltration of the first precursor can be performed simultaneously, with infiltration beginning immediately after the first precursor is supplied to the reaction chamber. The supply of the first precursor into the reaction chamber can be stopped before infiltration is stopped. For example, the first precursor can be supplied to the substrate by filling the reaction chamber with the first precursor and keeping the first precursor stationary in the reaction chamber for the infiltration period. The advantage of infiltration is that it reduces the consumption of the first precursor.

[0019] The first precursor can also be supplied to the substrate by continuously flowing the first precursor through the reaction chamber during the first period. The first precursor can also be supplied to the substrate by flowing, packing, and immersion, and / or any combination thereof.

[0020] The amount of photosensitizer in the unexposed photoresist layer can be increased by impregnating the unexposed photoresist layer on the substrate with a first precursor containing at least a portion of a photosensitizer that reacts sensitively to exposure radiation for a first period T1. For example, since the photosensitizer is insoluble in photoresist, the amount of photosensitizer in the photoresist can be limited before rotating the photoresist on the substrate. By impregnating a portion of the photosensitizer after rotating the unexposed photoresist layer on the substrate, an excess of photosensitizer can be supplied to the photoresist layer.

[0021] The photosensitizer can be uniformly penetrated throughout the entire depth of the photoresist. Alternatively, the photosensitizer can be penetrated at a higher concentration in the upper part of the photoresist and a lower concentration in the lower part. Additional photosensitizer can improve the sensitivity of the resist to exposure radiation in subsequent lithography exposures.

[0022] The photosensitizer can be permeated into the pores of the unexposed photoresist and / or diffused into the photoresist layer. The first precursor can react with the unexposed photosensitive layer to form an improved unexposed photoresist layer containing a photosensitizer that is sensitive to exposure radiation, or the first precursor can simply be absorbed into the unexposed photoresist. If the first precursor reacts with the unexposed photosensitive layer to form an improved unexposed photoresist layer containing a photosensitizer, the improved layer can be finished and transported to a lithography system for exposure in step 130.

[0023] In step 120b, a portion of the first precursor can be removed during a second period T2. This can be done by purging with an inert gas, such as nitrogen, and exhausting the gas from the reaction chamber, whereby all unreacted gas can be removed. Where the first precursor sufficiently reacts with the unexposed photosensitive layer to form a modified unexposed photoresist layer containing a photosensitizer, the modified layer can be finished and transported to a lithography system for exposure in step 130. Step 120b can be omitted if the first precursor completely reacts with the unexposed photoresist without any first precursor left in the reaction chamber, and / or if residual first precursor is acceptable in the environment of the reaction chamber.

[0024] If in step 120a only the first precursor is adsorbed into the unexposed photoresist, the second precursor can be supplied and permeated into the unexposed photoresist layer during a third period T3. The first and second precursors can react with each other to form a photosensitizer in the unexposed photoresist. Alternatively, the first precursor can react with the unexposed photosensitive layer and the second precursor to form a modified unexposed photoresist layer containing a photosensitizer.

[0025] Here again, the substrate can be transported to a lithography system for exposure, or the impreg nation cycle can comprise step 120d, in which a portion of the second precursor can be removed during a fourth period T4 before being transported to the lithography system in step 130. Step 120b can be omitted if the second precursor completely reacts with the unexposed photoresist without any first precursor left in the reaction chamber, and / or if residual first precursor is acceptable in the environment of the reaction chamber. The latter is the case, for example, where water, nitrogen or oxygen is used as the second reactant.

[0026] The infiltration sequence can be repeated N times via 140, where N is 1 to 60, preferably 1 to 10, most preferably 1 to 5, for example 1, 2, 3, or 4. The precursor is preferably a fluid, such as vapor or gas, during infiltration. The precursor may be evaporated from a liquid and / or sublimated from a solid precursor source. To ensure that there is sufficient fluid when supplying the precursor to the substrate in the reaction chamber, the precursor vapor or gas may be stored in a buffer volume.

[0027] Removal of the first and / or second precursor can be achieved by evacuating the first or second precursor from the reaction chamber and, alternatively or additionally, purging the first and / or second precursor by supplying a purge gas into the reaction chamber.

[0028] In step 120a, the first precursor can be infiltrated for a first period T1 of 1 to 20,000 seconds, preferably 5 to 6,000 seconds, more preferably 10 to 4,000 seconds, and most preferably 20 to 2,000 seconds. The exact period may depend particularly on the pressure and the volume of the reaction chamber. In this way, the first precursor can be deeply infiltrated into the unexposed photoresist layer.

[0029] In step 120b, a portion of the first precursor can be removed for a second period T2 of 1 to 20,000, preferably 20 to 6,000, more preferably 50 to 4,000, and most preferably 100 to 2,000.

[0030] The methods in steps 120a to 120d can be carried out in deposition / infiltration systems 200 (Figure 2) and 300 (Figure 3). This system may be a diffusion oven, a chemical vapor deposition system, an atomic layer deposition system, or a system specifically for sequential infiltration synthesis.

[0031] This method may include controlling the temperature of the reactor chamber to a temperature of 0 to 450°C, preferably 50 to 150°C, more preferably 60 to 110°C, and most preferably 65 to 95°C.

[0032] Referring here to Figure 2, a system 200 for penetrating at least a portion of an unexposed photoresist layer is illustrated. The system 200 may comprise a reactor 202 which may further comprise a first reaction chamber 203, a substrate holder 204, and a gas distribution system 206. The system 200 may also comprise a gas precursor supply system which may further comprise a first precursor supply source 207; a second precursor supply source 208; a carrier gas or purge gas supply source 210; and valves 211, 212, and 214 positioned between the supply sources 207, 208, 210 and 216 and the reactor 202.

[0033] The reaction chamber 203 may be a standalone reaction chamber or part of a cluster tool. Furthermore, the reaction chamber 203 may be dedicated to the infiltration process as described herein, or the reaction chamber 203 may be used for other processes, such as film deposition, removal of part of at least one polymer layer and one or more additional layer depositions, and / or etching processes. For example, the reaction chamber Chamber 203 can be equipped with reaction chambers typically used in chemical vapor deposition (CVD) and / or atomic layer deposition (ALD) processes, and can also be equipped with direct plasma and / or remote plasma devices.

[0034] Furthermore, the reaction chamber 203 can operate under vacuum or near atmospheric pressure. As an example, the reaction chamber 203 may comprise a reaction chamber suitable for ALD deposition of a film by continuously pulsed a first precursor and a second precursor onto at least one substrate. The reaction chamber may also be configured to allow at least the first precursor to penetrate into an unexposed photoresist layer material. An exemplary ALD reaction chamber suitable for system 200 is described in U.S. Patent No. 8,152,922, the contents of which are incorporated herein by reference to the extent that they are not inconsistent with this disclosure.

[0035] The substrate holder 204 can be configured to hold in place during the process at least one substrate, for example, substrate 216, on which an unexposed photoresist layer is placed. Additionally or alternatively, the substrate holder 204 may be heated, cooled (for example, by a heating element 205), or at the ambient process temperature during the process. In some embodiments, the heating element 205 may be configured to perform an annealing step on at least one substrate 216.

[0036] Although the gas distribution system 206 is illustrated in block form, the gas distribution system 206 is relatively complex and may be designed to mix vapors (gases) from the first precursor supply source 207, the second precursor supply source 208, and the purge gas from the gas supply source 210 before distributing the gas mixture to the rest of the reaction chamber 203. Furthermore, the gas distribution system 206 may be configured to provide a vertical or horizontal flow of gas to the semiconductor surface (as illustrated). An exemplary gas distribution system is described in U.S. Patent No. 8,152,922.

[0037] The first precursor source 207 can be a liquid, solid, or gas containing a portion of a photosensitizer suitable for the infiltration process. If the first precursor source 207 is a liquid or solid, the source material can be vaporized or sublimated before being placed in the reaction chamber 203.

[0038] The second precursor source 208 may be a liquid, solid, or gaseous source containing a material suitable for the infiltration process. If the second precursor source 208 is a liquid or solid, the source material may be vaporized or sublimated before entering the reaction chamber 203.

[0039] The first and second precursors can be used together to deposit and / or impregnate a photosensitizer into an unexposed photoresist layer. For example, in some embodiments, the system 200 may be configured to deposit and / or impregnate a photosensitizer containing a metal.

[0040] The metal in the photosensitizer can be selected from the group of alkaline earth metals. The metal in the photosensitizer may include magnesium and / or calcium.

[0041] The metal in the photosensitizer can be selected from the group including aluminum (Al), gallium (Ga), germanium (Ge), hafnium (Hf), zirconium (Zr), indium (In), lithium (Li), tellurium (Te), antimony (Sb), and tin (Sn). The improved unexposed photoresist layer may contain one or more metal oxides from these metals.

[0042] The first precursor may be a metal halide. The metal halide may be tin(IV) iodide (SnI4), also known as stannic iodide, or tin(IV) chloride (SnCl4), also known as tin tetrachloride or stannic chloride.

[0043] When impregnating with zirconium or hafnium, the Zr or Hf precursor may include a metal-organic precursor, an organometallic precursor, or a halide precursor. In some embodiments, the precursor is a halide. In some other embodiments, the precursor is an alkylamine compound of Hf or Zr, such as TEMAZ or TEMAH.

[0044] The metal to be impregnated may include aluminum oxide (Al2O3), aluminum nitride (AlN), zirconium oxide (ZrO2), or hafnium oxide (HfO2).

[0045] The first precursor may be a metal alkylamide precursor. The first precursor may include one or more of trimethylaluminum (TMA), triethylaluminum (TEA), and dimethylaluminum hydride (DMAH), tetraethyltin, tetramethyltin, or acetylacetonate tin. The permeating material contains aluminum as the metal.

[0046] The purge gas source 210 may include any suitable gas suitable for purging the first precursor source 207 and / or the second precursor source 208. The carrier gas or purge gas source 210 may also include any gas suitable for purging the reaction chamber 203 before, after, or during the deposition and / or infiltration process. According to exemplary embodiments of this disclosure, the purge gas may be nitrogen, argon, helium, or a combination thereof.

[0047] As illustrated in Figure 2, sources 207, 208, and 210 are in fluid communication with the reaction chamber 203 via valves 211, 212, and 214, and these valves can be used to control the flow, mixing, and distribution of the respective source substances to the reaction chamber 203 using supply lines 219, 220, and 222.

[0048] In further embodiments of the present disclosure, a system 300 for depositing and / or impregnating an unexposed photoresist layer is illustrated with reference to Figure 3. System 300 may be similar to that of system 200, but may comprise a reactor 302 which may further comprise a first reaction chamber 203A and a second reaction chamber 203B. Figure 3 illustrates a reactor 302 comprising two reaction chambers, but in some embodiments, as described above herein, the reactor 302 may comprise multiple reaction chambers, each reaction chamber comprising a substrate holder 204 and a gas distribution system 206. The substrate holder may be configured to hold a single substrate, 2 to 25 substrates (mini-batch), or 26 to 200 substrates (full batch). The system 300 may also include a first precursor supply source 207, a second precursor supply source 208, a carrier gas or purge gas supply source 210, and valves 211, 212, and 214 positioned between the supply sources 207, 208, and 210 and the reactor 302.

[0049] System 300 may also include a transport system 304 used to transport a substrate, such as a semiconductor, from the first reaction chamber 203A and the second reaction chamber 203B to the outside of the system. In some embodiments, the reaction chambers 203A and 203B may be dedicated to the infiltration process as described herein, or the reaction chambers 203A and 203B may be used for other processes, such as layer deposition and / or It may also be used in etching processes. For example, reaction chambers 203A and 203B may comprise reaction chambers typically used in chemical vapor deposition (CVD), infiltration and / or atomic layer deposition processes, as described herein. In further embodiments, system 300 may comprise additional reaction chambers for performing additional dedicated processes, such as deposition and etching processes.

[0050] As illustrated in Figure 3, sources 207 and 208 are in fluid communication with reactor 302 via valves 211 and 212, which can be used to control the flow, mixing, and distribution of each source material to reactor chambers 203A and 203B using supply lines 219 and 220 and all parts of a common precursor supply system 201. This method involves supplying substrates to each reaction chamber and supplying first and / or second precursors to at least two reaction chambers using the common precursor supply system 201.

[0051] This system may include a common precursor removal system 226 (e.g., a vacuum pump). The method may further include removing a first or second precursor from at least two reaction chambers using the common removal system 226.

[0052] This system may include common purge systems 210, 214, and 222. The method may include removing a first or second precursor from at least two reaction chambers by supplying a purge gas using a common purge system and / or a vacuum pump.

[0053] In one embodiment, the reaction chamber of the system 200 in Figure 2 is configured and positioned to accommodate a single substrate 21 in Figure 1, and can supply a first precursor for a first period T1 of 1 to 20,000, preferably 20 to 4,000, and more preferably 30 to 1,000 seconds.

[0054] In a further embodiment, the reaction chamber of the system is configured and arranged to accommodate 2 to 25 substrates and can supply a first precursor for a period T1 of 1 to 16,000, preferably 20 to 7,000, most preferably 30 to 1,500 seconds.

[0055] In another embodiment, the reaction chamber is configured and arranged to accommodate 26 to 200 substrates and can supply the first precursor for a period T1 of 1 to 20,000, preferably 100 to 10,000, more preferably 200 to 6,000, and most preferably 300 to 4,000 seconds. Larger reaction chambers facilitate more substrates but may result in longer process periods T1, T2, T3, or T4.

[0056] Before impregnating the unexposed photoresist layer with the penetration material, it may be advantageous to purge the reaction chamber for 1 to 3000 seconds, preferably 120 to 1200 seconds, at a temperature of 20 to 600°C, preferably 50 to 150°C, and most preferably 70 to 100°C, to improve degassing from the unexposed photoresist layer and cleaning of the reaction chamber.

[0057] In step 120a, the first precursor can be supplied using a bubbler for a first period T1, and a discontinuous flow of the first precursor is supplied by alternately performing pulses of the first precursor mixed with the purge gas for 0.1 to 100 seconds, preferably 1 to 3 seconds, and pulses of the purge gas for 0.1 to 20 seconds, preferably 0.3 to 1 second.

[0058] The first precursor is subjected to the reaction chamber pressure before supplying the precursor to the reaction chamber. The mixture can then be heated to a temperature between room temperature and the boiling point, preferably 20 to 450°C, more preferably 30 to 80°C, and even more preferably 35 to 60°C.

[0059] The infiltration system can be equipped with a temperature control system comprising a controller, heater, and temperature sensor to control the temperature inside the reaction chamber to 0 to 450°C, preferably 20 to 150°C, more preferably 60 to 110°C, and most preferably 65 to 95°C. The reactor chamber can be heated to a temperature of 20 to 450°C, preferably 50 to 150°C, more preferably 60 to 110°C, and most preferably 65 to 95°C. All surfaces inside the reactor chamber, exhaust line, and valve can be heated to 20 to 450°C, preferably 50 to 150°C, more preferably 60 to 110°C, and most preferably 65 to 95°C to avoid condensation of at least one of the precursors in the system.

[0060] The deposition / infiltration system can be equipped with a pressure control system comprising a controller, a pump, and a purge gas or first precursor supply unit to control the pressure in the reaction chamber. The pressure in the chamber can be controlled to a value of 0.001 to 1000 Torr, preferably 1 to 400 Torr, more preferably 2 to 100 Torr, and most preferably 4 to 50 Torr.

[0061] The second precursor may be an oxidizing agent. The oxidizing agent is selected from the group including water, ozone, hydrogen peroxide, ammonia, and hydrazine.

[0062] The second precursor can also be omitted. The first precursor may react, for example, with OH groups present in the resist. If the substrate is removed from the reactor because the second precursor is not needed, the first precursor may also react with moisture or oxygen from the ambient air.

[0063] To carry out the infiltration, a precursor for obtaining the metal, such as trimethylaluminum (TMA) and water (H2O) to form aluminum oxide (Al2O3, AlO), can be used. The infiltration in step 120a can be carried out at a temperature in the range of 20 to 300°C, and in the case of aluminum oxide formation, at a preferred temperature range of 65 to 95°C. The temperature during step 120c may be lower than the temperature during the previous stage, so a cooling step may be required to proceed from an exemplary annealing or gas release temperature of 250°C to the temperature of the second step 130 of 70 to 100°C. The temperature of any annealing or gas release process can be at least 25°C higher than the temperature of the second steps 120a to d, preferably 25 to 300°C higher than the temperature of the second step 120, or more preferably 100 to 250°C higher than the temperature of the second step 120.

[0064] The penetration of TMA in a single wafer reaction chamber at a pressure of approximately 8 Torr can be achieved by allowing the first precursor to penetrate for a period T1 ranging from 1 to 2000 seconds, preferably 2 to 600 seconds, more preferably 4 to 400 seconds, and most preferably 6 to 200 seconds. For example, at a pressure of approximately 8 Torr, a penetration time of 50 seconds can be achieved by filling the reaction chamber with the first precursor for 30 seconds and immersing the resist on the substrate while keeping the first precursor stationary in the reaction chamber for 20 seconds, yielding good results. It should be understood that these periods depend on the (partial) pressure of the first precursor, and the periods can be shortened by increasing the pressure.

[0065] Step 120b may also include removal and / or purging during a second period T2 of 0.01 to 10,000 seconds, preferably 1 to 6,000, more preferably 5 to 4,000, and most preferably 20 to 2,000 seconds. Removal and / or purging may be required to remove the first precursor from the reactor walls so that the particles in the reactor chamber can be freed. In an optimized reactor, other means may be used to prevent the first precursor from adhering to the walls. This can be prevented, and the removal / purging period can be shortened.

[0066] Step 120c may include supplying a second precursor, such as water, for a period T3 ranging from 1 to 10,000 seconds, preferably 2 to 800 seconds, and more preferably 4 to 100 seconds. The second step 120d may also include a second removal and / or purge for a fourth period T4 ranging from 0.01 seconds to 10,000 seconds, preferably 1 to 6,000 seconds, more preferably 5 to 4,000 seconds, and most preferably 20 to 2,000 seconds. Removal and / or purging may be required to remove the first precursor from the reactor walls so that the particles in the reactor chamber can be freed. In optimized reactors, the first precursor may not adhere to the walls by other means, and a shorter removal / purge period may be required.

[0067] Depending on the reaction between the first precursor and the photoresist, steps 120a and 120b may be omitted. If the substrate is removed from the reaction chamber, steps 120a and 120b may be omitted if the first precursor can react with the ambient atmosphere (e.g., moisture or oxygen in the ambient atmosphere).

[0068] Furthermore, steps 120a to 120d can be repeated as needed to obtain sufficient penetration of the metal or dielectric.

[0069] According to at least one embodiment of the present invention, a light bake can be performed before penetration to slightly degas / stabilize the resist.

[0070] According to at least one embodiment of the present invention, penetration can precede any step of annealing. In this case, the metal may first penetrate the unexposed photoresist layer material, and then the annealing process may be carried out. In at least one embodiment of the present invention, any annealing and penetration steps can be carried out without any exposure to ambient air.

[0071] The specific embodiments shown and described are illustrative of the present invention and its best mode, and are not intended to limit the scope of the aspects and embodiments in any way. In fact, for the sake of brevity, conventional manufacturing, association, preparation, and other functional aspects of the system may not be described in detail. Furthermore, the connecting lines shown in various figures are intended to represent exemplary functional relationships and / or physical connections between various elements. Many alternative or additional functional relationships or physical connections may exist in the actual system and / or may not exist in some embodiments.

[0072] It should be understood that the configurations and / or methods described herein are illustrative in nature, and these particular embodiments or examples should not be considered restrictively, as many variations are possible. The specific routines or methods described herein may represent one or more of any number of processing methods. Therefore, the various operations illustrated may be performed in other sequences, or may be omitted in some cases, within the illustrated sequence.

[0073] The subject matter of this disclosure includes all novel and non-obvious combinations and partial combinations of the various processes, systems, and configurations disclosed herein, as well as other features, functions, operations, and / or characteristics, and any and all equivalents thereof.

Claims

1. A method for forming an improved unexposed photoresist layer with increased sensitivity to exposure radiation from an unexposed photoresist layer on a substrate, wherein the improved unexposed photoresist layer The unexposed photoresist layer is provided on the substrate within the reaction chamber, The first precursor is supplied to the substrate in the reaction chamber, thereby allowing the first precursor to permeate the unexposed photoresist layer on the substrate during a first period T1, thereby forming the material. The first precursor comprises a first material containing at least a portion of a photosensitizer that reacts sensitively to exposure radiation, The photosensitizer comprises aluminum and / or tin. The first precursor consists of one or more of trimethylaluminum (TMA), triethylaluminum (TEA), dimethylaluminum hydride (DMAH), tetraethyltin, tetramethyltin, and acetylacetonate tin. The improved unexposed photoresist layer comprises an aluminum and / or tin oxide after penetration with the photosensitizer, in a method.

2. The method according to claim 1, wherein the first precursor reacts with the unexposed photoresist layer to form the improved unexposed photoresist layer containing the photosensitizer that is sensitive to exposure radiation.

3. The aforementioned permeation cycle is A portion of the first precursor is removed from the reaction chamber during the second period T2, The method according to claim 1, further comprising supplying a second precursor to the unexposed photoresist layer on the substrate in the reaction chamber, thereby allowing the second precursor to permeate the unexposed photoresist layer on the substrate for a third period T3.

4. The method according to claim 3, wherein the first and second precursors react with each other to form a photosensitizer in the unexposed photoresist layer that is sensitive to exposure radiation.

5. The method according to claim 3, wherein the first precursor reacts with the unexposed photoresist layer and the second precursor to form the improved unexposed photoresist layer containing the photosensitizer that is sensitive to exposure radiation.

6. The aforementioned permeation cycle is The first precursor is to permeate for the first period T1, The first precursor is removed during the second period T2, The second precursor is to permeate during the third period T3, The method according to claim 3, comprising removing the second precursor for a fourth period T4, wherein the infiltration cycle is repeated 1 to 60 times.

7. The method according to claim 6, wherein the first period T1 is longer than the second period T2.

8. The method according to claim 3, wherein the first period T1 is 0.1 to 10,000 times the second period T2.

9. The method according to claim 1, wherein the substrate material comprises a mask layer beneath the unexposed photoresist layer.

10. The method according to claim 1, wherein the temperature of the reactor is controlled to a value of 0 to 450°C, preferably 20 to 150°C, before the first precursor is impregnated into the unexposed photoresist material.

11. The method according to claim 1, wherein the pressure in the chamber is 0.001 to 1000 Torr.

12. The method according to claim 6, wherein the first period T1 is longer than the third period T3.

13. The method according to claim 1, wherein the improved photosensitizer is sensitive to exposure to EUV radiation.

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