Sequential infiltration synthesis apparatus

Continuous infiltration synthesis device

SEQUENTIAL INFILTRATION SYNTHESIS APPARATUS

The present invention generally relates to apparatus and methods for manufacturing electronic components. More particularly, the present invention relates to the formation of structures or layers on substrates using infiltration devices.

As the trend has made semiconductor elements smaller and smaller, different patterning techniques have emerged. These techniques include spacer-defined quadruple patterning, extreme ultraviolet lithography (EUV), and EUV in combination with spacer-defined double patterning. In addition, directed self-assembly (DSA) has been considered as an option for future lithography applications. DSA involves the use of block copolymers to define self-assembled patterns. The block copolymer used may include poly(methyl methacrylate) (PMMA), polystyrene or poly(styrene-block-methyl methacrylate) (PS-b-PMMA). Other block copolymers can include emerging "high-chi" polymers that can potentially enable smaller sizes.

The patterning techniques described above can utilize permeable materials such as EUV polymer or DSA block copolymer resists disposed on the substrate to achieve high-resolution patterning of the substrate. To meet both high resolution and line edge roughness requirements, the polymeric resist can be a thin layer. However, such thin layers of polymer resist can have several disadvantages. In particular, high-resolution polymer resists may have low etch resistance and may suffer from high line edge roughness. This low etch resistance and high line edge roughness can make transfer to the bottom layer more difficult.

Accordingly, it may be advantageous to infiltrate a permeable material, such as a patterned material resist, to alter the properties of the permeable material. To perform infiltration, an infiltration device with a tunable infiltration process may be advantageous.

According to at least one embodiment of the present invention, there is provided a continuous infiltration apparatus including a continuous infiltration synthesis apparatus comprising: a reaction chamber constructed and configured to hold at least one first substrate; precursor distribution and removal a system that provides the gaseous first or second precursor to the reaction chamber and removes the gaseous first or second precursor from the reaction chamber; and a sequencer operably connected to the precursor distribution and removal system and Contains a memory provided with a program that, when running on a sequencer, performs the infiltration of the permeable material disposed on the substrate by activating the precursor distribution and removal system to dispose the first precursor and maintained in the reaction chamber for a first period of time T1; activate the precursor distribution and removal system to remove a portion of the first precursor from the reaction chamber for a second period of time T2; and activate the precursor distribution and removal system to remove the first precursor from the reaction chamber; The two precursors are disposed and maintained in the reaction chamber for a third period of time T3. The program in the memory can be programmed longer than the first period T1 of the second period T2. The first period of time T1 in which the first precursor is placed may be programmed to be longer than the second period of time T2 in which a portion of the first precursor is removed to allow sufficient time for the first precursor to penetrate deeply into the permeable material.

The second period of time T2 can be programmed long enough to remove the first precursor from the reaction chamber and from the surface of the permeable material to ensure that only the first precursor permeates the permeable material and no significant deposition on the permeable material.

The second period of time T2 may be programmed long enough to remove the first precursor from the reaction chamber, from the surface of the permeable material, and partially from pores in the permeable material. The depth of penetration can be tuned in this way.

According to another embodiment, a continuous infiltration synthesis apparatus is provided, comprising: a reaction chamber constructed and configured to hold at least a first substrate; a precursor distribution and removal system, which provides to the reaction chamber a vaporized first or a second precursor and removes the vaporized first or second precursor from the reaction chamber; and a sequencer operably connected to the precursor distribution and removal system and including a memory provided with a program, the The infiltration of the permeable material disposed on the substrate is performed by the program running on the sequencer by activating the precursor distribution and removal system to dispose and maintain the first precursor in the reaction chamber for the first period T1; activating the precursor distribution and removal system to remove a portion of the first precursor from the reaction chamber for a second period T2; and activating the precursor distribution and removal system to dispose and maintain the second precursor in the reaction chamber for a third time period T3.

A program in memory is programmed to execute during a first period T1: activate the precursor distribution and removal system to close the gas removal flow path and place the first precursor in the reaction chamber for the continuous loading period LP; and activate A precursor distribution and removal system to close the first precursor flow path and maintain the first precursor in the reaction chamber while keeping the removal flow path closed for the soaking period SP. In this way, economical use of the first precursor can be ensured during a longer first period of time that may be necessary for the infiltration process.

According to another embodiment, there is provided a method of forming a patterned structure or layer with a continuous infiltration synthesis device, wherein the method comprises: disposing a substrate having a patterned permeable material on top of a reaction chamber; and at least one infiltration Infiltrating the patterned infiltrating material with the infiltrating material in the cycle. The infiltration cycle includes: activating the precursor distribution and removal system to dispose and maintain the first precursor in the reaction chamber for a first period of time T1; activating the precursor distribution and removal system to remove the first precursor from the reaction chamber a portion for a second period T2; and activating the precursor distribution and removal system to place and maintain the second precursor in the reaction chamber for a third period T3. The first period T1 is longer than the second period T2. The patterned permeable material may be a patterned photoresist or DSA material.

The first period T1 may include: closing the gas removal flow path and disposing the first precursor in the reaction chamber for the loading period LP; and closing the first precursor flow path and maintaining the first precursor in the reaction chamber while removing the first precursor Except that the flow path remains closed for the soaking period SP.

Accordingly, the continuous infiltration synthesis device comprises: a first evaporator constructed and configured to vaporize hydrocarbon-containing compounds; a second evaporator constructed and configured to vaporize metal halide-containing compounds; precursor distribution and migration In addition to a system constructed and configured to provide a reaction chamber with vaporized first precursor from one of the first or second vaporizers, and second vaporized from the other of the first and second vaporizers precursors and removing the first and second precursors from the reaction chamber; and a sequencer operably connected to the precursor distribution and removal system and including a memory provided with a program that controls the sequence The infiltration of the permeable material is performed on-device by: activating the precursor distribution and removal system to place the first precursor on the permeable material on the substrate in the reaction chamber for a first period of time T1; activating the precursor a bulk distribution and removal system to remove a portion of the first precursor from the reaction chamber for a second period of time T2; and activating the precursor distribution and removal system to dispose the second precursor on the permeable substrate in the reaction chamber The material lasts for a third period T3. The first vaporizer may be constructed and configured to vaporize the metal hydrocarbon compound. The second vaporizer can be constructed and configured to vaporize the metal halide compound. The reaction between the permeable material, the metal hydrocarbons and the metal halide ensures that the amount of metal permeable to the metal can be optimized. The amount of metal infiltrated can set the desired etch resistance.

For purposes of summarizing the objects of the present invention and the advantages achieved over the prior art, certain objects and advantages of the present invention have been described herein above. Of course, it should be understood that not all such objects or advantages may be achieved in accordance with any particular embodiment of the present invention. Thus, for example, one skilled in the art recognizes that the present invention may be embodied in a manner that achieves or optimizes one advantage or group of advantages taught or suggested herein without achieving other objects or advantages that may be taught or suggested herein. or implement.

All such specific examples are intended to be within the scope of the invention disclosed herein. These and other embodiments will become apparent to those skilled in the art from the following detailed description of certain embodiments with reference to the accompanying drawings, but the invention is not limited to any specific embodiments disclosed.

<p>2: Reaction chamber</p><p>3: Precursor distribution and removal system</p><p>5: Precursor distribution and removal system</p><p>10: Substrate holder</p><p>12: Substrate</p><p>14: The first heating member</p><p>16: Heating controller</p><p>18: Precursor pipeline</p><p>19: Distributed reaction chamber valve</p><p>20: First Precursor Valve</p><p>22: Second Precursor Valve</p><p>24: Purge valve</p><p>26: Temperature sensor</p><p>28: First Precursor</p><p>29: Second Precursor</p><p>30: Container</p><p>31: Container</p><p>32: First Precursor Heater</p><p>33: Second Precursor Heater</p><p>34: Purge gas</p><p>36: Reaction chamber valve</p><p>39: Gas removal pump</p><p>40: Sequence controller</p><p>50: Steps</p><p>51: Infiltration method</p><p>52: Steps</p><p>53: Steps</p><p>54: Steps</p><p>55: Steps</p><p>56: Steps</p><p>57: Steps</p><p>58: Steps</p><p>59: Alternative Shortcuts</p><p>60: Alternative Shortcuts</p><p>66: entry port</p><p>67: Opening</p><p>68: Edge</p><p>69: Sprinkler</p><p>70: Batch reaction chamber</p><p>71: Boat</p><p>71A: Bottom part</p><p>72: Entrance</p><p>73: Export</p><p>M: memory</p><p>FP: Flush Period</p><p>LP: Loading period</p><p>SP: Soaking period</p>

It will be appreciated that components in the drawings are shown for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the components in the figures may be exaggerated relative to other components to help improve understanding of the illustrated embodiments of the invention.

Figure 1 depicts a continuous infiltration synthesis apparatus according to one embodiment.

Figures 2a and 2b illustrate an infiltration routine that may be performed by the continuous infiltration device of Figure 1, according to at least one embodiment.

Figure 3 depicts the reaction chamber of a continuous infiltration device according to one embodiment.

Figure 4 depicts the reaction chamber of a continuous infiltration device according to another embodiment.

5 depicts a reaction chamber of a continuous infiltration device comprising a batch reactor, according to one embodiment.

6 illustrates an infiltration program that may be performed by the continuous infiltration device of FIG. 1 with an additional precursor supply system, according to at least one embodiment.

Figures 7a-7d show Secondary Ion Mass Spectrometry (SIMS) measurements on layers infiltrated on continuous infiltration devices with different infiltration formulations.

Figures 8a and 8b depict cross sections of patterns infiltrated on continuous infiltration devices with different infiltration formulations.

Although specific examples and embodiments are disclosed below, those skilled in the art will understand that the invention extends beyond the specifically disclosed examples and/or uses and obvious modifications and equivalents thereof. Therefore, it is intended that the scope of the disclosed invention should not be limited by the specific disclosed embodiments described below.

Figure 1 depicts a continuous infiltration synthesis apparatus according to one embodiment. The device comprises a reaction chamber 2 made of a suitable material such as steel, aluminium or quartz. The substrate 12 provided with the permeable material on top can be placed on the substrate holder 10 in the reaction chamber 2 by a substrate handler through a substrate opening (not shown). The reaction chamber 2 forms a chamber closed at one end by a flange, gas is introduced into the reaction chamber through one or more openings provided with at least one (distribution) reaction chamber valve 19 to control the opening and closure. The distribution reaction chamber valve 19 places the liquid distribution portion of the precursor distribution and removal systems 3 , 5 close to the reaction chamber 2 .

The precursor distribution and removal systems 3 , 5 can dispose the first precursor 28 or the second precursor 29 in the reaction chamber via the distribution reaction chamber valve 19 . The first precursor 28 may be introduced into the chamber 2 as a gas by evaporating the liquid or solid contained in the vessel 30 using the first precursor heater 32 to set a sufficient vapor pressure for delivery into the chamber 2 . The first precursor heater 32 may provide heat to the first precursor in the vessel 30 . Likewise, the second precursor 29 may be introduced into the chamber 2 as a gas by evaporating the liquid or solid contained in the vessel 31 using the second precursor heater 33 to set a sufficient vapor pressure for delivery into the reaction chamber 2 middle. Although the depicted flow paths of the first and second precursors may be partially shared, they may also be partially or completely separate. In the case of separated flow paths, each flow path may be provided with a separate distributed reaction chamber valve 19 .

The precursor distribution and removal systems 3 , 5 may include a flushing system to provide flushing gas 34 to the reaction chamber 2 via the flushing valve 24 and the distribution reaction chamber valve 19 . The flushing gas can be an inert gas such as nitrogen and can be used to flush the reaction chamber 2 . As depicted in the flow path of the purge gas, although the first and second precursors may be partially shared, they may also be partially or completely separate. In the case of separated flow paths, each flow path may be provided with a separate distributed reaction chamber valve 19 .

Alternatively or additionally, the flushing system may be constructed and configured to place the flushing gas directly in the reaction chamber 2 via a flushing reaction chamber valve (not shown) that provides the flushing gas directly in the reaction chamber 2 . By placing the flushing gas directly in the reaction chamber, it becomes possible to use a precursor distribution and removal system to load the precursor while flushing the reaction chamber. In this way it is possible to increase the output.

Alternatively, a separate exhaust (not depicted) from the precursor line 18 to the pump 39 may be used to more efficiently flush the precursor line 18 while closing the distributed reaction chamber valve 19 .

The reaction chamber may be closed at the other end by a flange connected to the gas removal component of the precursor distribution and removal system via one or more openings provided with one or more reaction chamber valves 36, such as gate valves. The gas removal pump 39 may be part of the gas removal portion of the precursor distribution and removal system.

The reaction chamber 2 may be provided with an opening (not shown) to set the substrate to the substrate holder 10 . A door may be provided to close and open an opening to be provided by the substrate handler in proximity to the substrate holder 10 . The substrate holder can also form part of the reaction chamber 2 and can be moved in a downward direction to be placed close to the substrate holder 10 by the substrate handler.

The first precursor 28 may be a compound having elements of the infiltrating material in the infiltrating material formed on the substrate 12 . The first precursor 28 may be disposed in the reaction chamber 2 through the first precursor valve 20 and the distribution reaction chamber valve 19 . Figure 1 illustrates a system with two vessels 30 and 31 each containing first and second precursors 28 and 29, respectively. However, the type of infiltrating material formed will determine the number of precursors and containers. For example, if a ternary infiltrating material is desired, the device may include three containers and three precursor valves. Containers 30 and 31 can optionally be bottles or other sources of precursors. For example, if one of the precursors may be solid, a particularly suitable vessel may be provided to accelerate the sublimation of the solid precursor. One of the vessels 30, 31 may also be provided with a gaseous precursor so that no heating is required.

A sequencer 40 (eg, a microcontroller) is operably connected to one or more of the reaction chamber valves 19 , 36 , the precursor valves 20 , 22 and the flush valve 24 . The sequencer 40 includes a memory M for storing programs to enable the device to infiltrate the permeable material on the substrate 12 disposed in the reaction chamber 2 with the first precursor 28 and the second precursor 29 . The temperature sensor 26 can monitor the reaction chamber temperature. The temperature sensor 26 may likewise be provided with a pressure sensor. A temperature sensor is operatively connected to the sequencer 40 to optimize process conditions for infiltration. Programs in memory M of sequencer 40 can be programmed to sequence the opening and closing of valves 19, 20, 22, 24 and 36 at the appropriate times to set and remove the first and second precursors to reaction chamber 2.

The device may be provided with a heating system comprising a first heating member 14 (eg, a heating resistance wire) and a heating controller 16 and operatively connected to a temperature sensor 26 . One or more of the temperature sensors 26 may likewise be provided with pressure sensors. The heating controller is operably connected to the sequence controller 40 . The temperature sensor 26 may be used to measure the temperature in the reaction chamber 2 and provide feedback on this temperature to the heating controller 16 to adjust the temperature of the heating member 14 and thus the temperature of the reaction chamber 2 . Additional temperature sensors may be present to control the temperature in the reaction chamber 2 and/or in the precursor distribution and removal system, thereby setting up multi-zone temperature control in the device.

One or more of the temperature sensors 26 may likewise be provided with pressure sensors. A pressure sensor may be operably connected to the sequencer 40 to adjust the process sequence based on the measured pressure.

The precursor feed flow conduit between the (distribution) reaction chamber valve 19 and the reaction chamber 2 may be provided with a portion of the heating member 14 . This portion of the heating member 14 along the precursor feed flow conduit can be individually controlled with temperature sensors 26 and heating controllers 16 extending in the conduit to regulate the temperature of the precursor feed flow conduit.

The precursor removal flow conduit between the reaction chamber 2 and the (removal) reaction chamber valve 36 may be provided with a portion of the heating member 14 . This portion of the heating member 14 along the precursor removal flow conduit can be individually controlled with a temperature sensor 26 and heating controller 16 extending in the precursor removal flow conduit.

In this way, cold spots can be avoided, which can lead to condensation in the reaction chamber 2, the precursor feed flow conduits and the precursor removal flow conduits. Condensation of the precursor can result in the precursor not being able to exit the reaction chamber efficiently in a timely manner, and thus the condensate can react with subsequent precursors to form particles that can contaminate the reaction chamber and substrate 12 . In particular, particles in the flow path that transport the precursor can cause a variety of problems.

The temperature can be set to the optimum process temperature. The speed of the infiltration process can be scaled by pressure and time during which the first or second precursors infiltrate the infiltrated material on the substrate: infiltration proceeds faster at higher temperatures. The process at higher pressures therefore advantageously reduces process time and maximizes throughput but increases the risk of condensation. The optimum process temperature should be higher than the boiling point temperature of the first or second precursor at the maximum pressure of the first or second precursor in the reaction chamber 2 to avoid condensation. By controlling the temperature from the reaction chamber 2 up to at least one of the reaction chamber valves 19, 36, the risk of condensation can be minimized.

For example, if the first or second precursor is trimethylaluminum (TMA), the vapor pressure is: 20°C-9 Torr; 40°C-25 Torr; 60°C-64 Torr; 80°C-149 Torr; 100°C~313 Torr; 128°C~760 Torr.

From these values it can be seen that the process pressure can be substantially increased by increasing the temperature in the reaction chamber. However, if a small fraction is present in a device that is in contact with the precursor and has a slightly lower temperature, there is an immediate risk of unwanted precursor condensation.

The interaction of the TMA precursor with the permeable material can occur primarily via adsorption and diffusion. Since the rates of adsorption and diffusion and the balance of adsorption reactions can be affected by changes in temperature, temperature can have a significant effect on infiltration.

The infiltration process can be optimal at 90°C, while at 120°C and 150°C, infiltration is less suitable for TMA. This is expected for adsorption-based treatments. At higher temperatures, the equilibrium of the adsorption reaction can be shifted towards the individual TMA and polymer species. Therefore a process temperature of between 20°C and 450°C, preferably between 50°C and 150°C, more preferably between 60°C and 110°C and optimally between 65°C and 95°C is preferred.

The heating system can be constructed and configured to control the temperature of the reaction chamber and the piping from the reaction chamber to at least its corresponding reaction chamber valve between 20°C and 450°C, preferably between 50°C and 150°C, more preferably at Between 60°C and 110°C and optimally between 65°C and 95°C. The sequencer may be constructed and configured to achieve and/or maintain the pressure of the first or second precursor in the reaction chamber during infiltration between 0.001 and 1000 Torr, preferably between 1 and 400 Torr, more Preferably between 5 and 100 Torr and most preferably between 10 and 50 Torr to avoid condensation. In this way, we generate sufficient safety tolerances to avoid condensation in the device, while having optimal process temperatures and pressures for using the precursor TMA.

The apparatus may include a direct liquid injector (DLI) with a liquid flow controller and a vaporizer. The liquid flow controller can control the flow of liquid to the vaporizer to vaporize the first or second precursor. It may not be necessary to heat the liquid flowing between the flow controller and the evaporator. The vaporizer can be heated to vaporize the first or second precursor. The heating system 16 may be constructed and configured to control the temperature of the reaction chamber 2 to the evaporator to the boiling temperature of the first or second precursor under the pressure of the first or second precursor in the reaction chamber to avoid condensation. The vaporizer can be constructed and configured in the reaction chamber to place the vaporized precursor directly in the reaction chamber. Evaporators can also be constructed and configured in a device precursor distribution and removal system.

The precursor distribution and removal system may include a bubbler for setting the precursor. The bubbler may be provided with a discontinuous precursor flow with pulses of the first precursor of 0.1 to 200, preferably 1 to 3 seconds, alternating with pulses of the mixed gas of 0.01 to 30, preferably 0.3 to 1 second.

Referring to FIG. 1 , during a typical operation, the first precursor 28 is infiltrated into the permeable material on the substrate by exposing it from the container 30 to the first precursor 28 in the gas phase. The first precursor 28 can react with the permeable material on the substrate and become a chemisorbed or physisorbed derivative that permeates the permeable material on the substrate. The second precursor 29 is then infiltrated into the permeable material on the substrate by exposure from the container 31 to the second precursor 29 in the gas phase. The second precursor 29 can react with a chemisorbed or physisorbed derivative of the first precursor 28 infiltrated in the infiltrated material on the substrate to become the final infiltrated material.

The containers 30, 31 for storing the first or second precursor can store metal alkyl compounds or boron alkyl compounds. The metal can be aluminum and the alkyl compound can be selected from the group consisting of trimethylaluminum (TMA), triethylaluminum (TEA), and dimethylaluminum hydride (DMAH).

The containers 30, 31 for storing the first or second precursor can store metal halide compounds, the metal halide compounds can be titanium (IV) chloride (TiCl), tantalum (V) chloride (TaCl)₅) and/or niobium chloride (NbCl₅)。

For infiltration of zirconium or hafnium, vessels 30, 31 may be constructed and configured to store Zr or Hf precursors. The Zr or Hf precursors may comprise metal-organic precursors, organometallic precursors or halide precursors. In some embodiments, the precursor is a halide, such as zirconium (IV) chloride (ZrCl₄) or HfCl₄, Hafnium (IV) chloride. In some other embodiments, the precursor is an alkylamine compound of Hf or Zr, such as TEMAZ or TEMAH.

The vessel 30, 31 for storing the first or second precursor may store an oxidizing agent selected from the group comprising oxygen, water or hydrogen peroxide, or a nitride selected from the group comprising ammonia and hydrazine. Oxygen O₂and water can be supplied by the supply line. Ozone O₃Available oxygen O₂Supply line and ozone generator to generate.

The apparatus may comprise: a first vessel 30 for containing a first or second precursor, such as aluminum or a boron hydrocarbon compound preferably selected from the group consisting of: trimethylaluminum (TMA), triethyl Aluminum (TEA) and Dimethylaluminum Hydride (DMAH) Dimethylethylamino alane (DMEAA), Trimethylamino alane (TEAA), N-methylpyrrolidine alane (MPA), Trimethylamine alane (MPA) - isobutylaluminum (TIBA), tri-tert-butylaluminum (TTBA) trimethyl boron and triethyl boron; and a second container 31 for containing the other of the first and second precursors , such as metal halides preferably from the group consisting of: titanium (IV) chloride (TiCl), tantalum (V) chloride (TaCl)₅) and niobium chloride (NbCl)₅). the latter Can be preferably used to infiltrate metal carbide materials.

Figures 2a and 2b illustrate an infiltration method according to at least one embodiment of the present invention for use in the device of Figure 1 . The method includes a first step 50 of disposing a substrate in the reaction chamber with a substrate handler, the substrate having at least one permeable material on the substrate.

The permeable material may be porous. Porosity can be measured by measuring the void space in the permeable material as a fraction of the total volume of the permeable material and can have a value between 0 and 1. A permeable material may be defined as porous if the fraction of void space within the total volume is greater than 0.1, greater than 0.2, or even greater than 0.3.

In one embodiment, the permeable material may be a patterned layer (eg, a patterned resist layer). The resist layer can be annealed. The annealing step may have the purpose of removing moisture or other contaminants from the resist, hardening the resist, selectively burning off portions of the resist from the substrate surface, or creating a desired porosity.

In one embodiment, the patterned layer can be provided by having a block copolymer film and promoting directional self-assembly of the block copolymer film to form the patterned layer. Infiltration of such patterned layers can improve the quality of such patterned layers. Block copolymer films can, for example, have lower etch resistance and the etch resistance of the pattern can be improved by infiltrating the pattern into the copolymer.

In one embodiment, the patterned layer can be provided by exposing the photoresist with a lithographic device. Infiltration of such patterned layers can improve the quality of such patterned layers. The patterned photoresist layer can, for example, have lower etch resistance and the etch resistance of the pattern can be improved by infiltrating the patterned photoresist.

In one embodiment, the infiltrated material may be a polymer that fills gaps or openings in the structure, which is then transferred to the metal oxide or metal by infiltration. The polymer can be already based on A polymer that is region-selectively grown on a specific surface on a plate, such as the bottom of a gap. The polymer layer can be annealed. The annealing step may have the purpose of removing moisture or other contaminants from the polymer, hardening the polymer, selectively burning off portions of the polymer from the substrate surface, or creating a desired porosity.

During step 50 in FIG. 2a, after the substrate is placed in the reaction chamber 2 in FIG. 1, the reaction chamber and the substrate can be cleaned by the memory M in the sequencer 40 knowing the program so that the removal pump 39 will react Room 2 was evacuated. Optionally, purge gas 34 may be provided with a purge system to purge reaction chamber 2 via purge valve 24 and distributed reaction chamber valve 19 and/or reaction chamber 2 may be heated to enhance venting. The program in memory M can be programmed to activate the precursor distribution and removal system to remove gas from the reaction chamber 2 and set the purge gas with the flush system so that the reaction chamber is flushed for 1 to 4000 seconds before infiltration begins, compared to Optimum 100 to 2000 seconds. Programs in memory M can be programmed to activate heater system 16 to heat reaction chamber 2 to between 20°C and 450°C, preferably between 50°C and 150°C and optimally at 70°C and 100°C to enhance polluting exhaust.

Subsequently, the memory M of the sequencer 40 may be provided with a program that, when executed on the processor of the sequencer 40, causes the infiltrating device to perform the infiltration method 51, in which the infiltrated material may be in one or more Infiltrated by infiltrating material during each infiltration cycle. Each infiltration cycle may include the following steps:

Step 52 includes disposing the first precursor on the infiltrated material on the substrate in the reaction chamber for a first period of time T1. The memory M of the sequencer 40 may be provided with a program that, when executed on the processor of the sequencer 40, causes the infiltration device to close the flush valve 24 and the distribution chamber valve 19 and by opening the first precursor valve 20 and utilizing the activated first precursor temperature controller 32 to heat the vessel 30 to vaporize the first precursor 28 from the first vessel 30 Instead, the first precursor accumulates in the conduits of the precursor distribution and removal system upstream of valve 19 in the distribution reaction chamber. The program in the memory M of the sequencer 40 can then be programmed to open the valve 19 for a shorter period of time to deliver the first precursor 28 to the reaction chamber 2 .

This can be done with the removal chamber valve 36 open and the removal pump activated for a flush period FP to flush the reaction chamber 2 with the first precursor, but this can also be omitted. When reaction chamber 2 is constructed and configured to accommodate a single substrate, then the program in memory can be programmed to activate the precursor distribution and removal system for a duration of 1 to 60, preferably between 2 and 30 seconds Flushing period FP. When the reaction chamber is constructed and configured to hold 2 to 25 substrates, the program in the memory can be programmed to have a rinse period of between 1 to 100, preferably between 2 and 50 seconds. When the reaction chamber is constructed and configured to hold 26 to 200 substrates, the program in the memory is programmed to have a flush period FP between 1 and 100, preferably between 5 and 50 seconds.

The first precursor can also be provided in the reaction chamber 2 by the precursor distribution and removal system while closing the removal chamber valve 36 by using a program installed in the memory M of the sequencer 40 without using the removal pump 39 Any precursors are removed for the loading period LP. This causes the pressure of the first precursor to build up in the reaction chamber 2 . When the pressure of the first or second precursor in the reaction chamber 2 reaches the desired process pressure (preferably between 0.001 and 1000 torr, preferably between 1 and 400 torr, more preferably between 5 and 100 Torr and optimally between 10 and 50 Torr), this accumulation can be terminated by the sequencer 40. Alternatively, there may be a pressure relief valve that opens when the pressure in the reaction chamber increases beyond a predetermined desired process pressure (which may also end the loading period LP).

Subsequently, the first precursor may remain stationary in the reaction chamber 2, while the precursor distribution and removal system does not dispose or remove any precursor during the soaking period SP. This can be done by the sequencer 40 to close the reaction chamber valve according to the program stored in the memory M of the sequencer 40 Doors 19 and 36 to proceed. When the reaction chamber 2 is constructed and configured to accommodate a single substrate, the program in the memory M can be programmed to activate the first precursor flow controller for between 1 and 3000 seconds, preferably between 3 and 1000 seconds , preferably a loading period LP between 5 and 500 seconds; and a soaking period SP between 10 and 9000 seconds, preferably between 50 and 5000 seconds and more preferably between 100 and 1000 seconds. When the reaction chamber 2 is constructed and configured to accommodate 2 to 25 substrates, the program in the memory of the sequencer may be between 1 and 3000 seconds, preferably between 3 and 1000 seconds, more preferably between 5 and 500 seconds A loading period LP between seconds; and a soaking period SP between 10 and 12000 seconds, preferably between 15 and 6000 seconds and more preferably between 20 and 1000 seconds. When the reaction chamber 2 is constructed and configured to hold 26 to 200 substrates, the program in the memory M can be programmed to have between 1 and 3000 seconds, preferably between 3 and 1000 seconds, more preferably 5 A loading period LP to 500 seconds; and a soaking period SP between 10 and 14000 seconds, preferably between 50 and 9000 seconds, more preferably between 100 and 5000 seconds and most preferably between 100 and 800 seconds.

Therefore, the first period T1 may include a flushing period FP, a loading period LP and/or a soaking period SP. During the entire time period T1, the first precursor may infiltrate and absorb in the infiltrating material. In step 52, the memory M of the sequencer 40 may be programmed with a program that, when executed on the processor of the sequencer, will cause the infiltration device to set the first precursor for between 1 and 20,000, Preferably between 20 and 6000, more preferably between 50 and 4000, and most preferably between 100 and 2000 seconds for the first period T1. In this way a deep penetration of the first precursor into the permeable material is ensured.

In step 53, a portion of the first precursor is removed for a second period of time T2. A program in the memory M of the sequencer 40 can open the removal chamber valve 36 to remove the first precursor from the reaction chamber 2 with the vacuum pump 38 . Additionally or alternatively, flushing can be set up with a flushing system The gas 34 is used to flush the reaction chamber 2 by opening the flush valve 24 and the distribution chamber valve 19 with the sequencer 40 .

The program in the memory M of the sequential flow controller 40 may be programmed by a program that, when executed on the processor of the sequential flow controller 40, causes the infiltration device to have a second time period T2 than the portion of the first precursor removed A longer time period T1 where the first precursor is placed in the permeable material. The program in the memory M can be programmed for the first period T1 which is 2 to 10000 times longer than the second period T2, preferably 5 to 2000 times longer, and more preferably 10 to 1000 times longer. The program in memory M can be between 0.1 and 3000 seconds, preferably between 3 and 100 seconds, more preferably between 6 and 50 seconds, even better between 8 and 30 seconds and the best programmed for a second time period T2 between 10 and 25 seconds.

In step 53, the second period of time T2 may only be sufficient to remove the first precursor from the reaction chamber, eg, 0.1 to 50 seconds, preferably 1 to 10 seconds. In this way there is infiltration of the permeable material and there is deposition on the permeable material.

Alternatively, the second period of time T2 may be selected only long enough to remove the first precursor from the reaction chamber and from the surface of the permeable material. For example, at T2 of 1 to 1000 seconds, preferably 8 to 100 seconds, there may be only infiltration of the first precursor in the resting permeable material and no significant deposition remains in the permeable material after step 53 is completed on the surface.

Alternatively, in step 53, the second period of time T2 can be selected to be long enough (eg, 2 to 3000 seconds, preferably 30 to 100 seconds) to infiltrate from the reaction chamber, from the surface of the permeable material, and from the permeable material The portion of the first precursor removes the first precursor. In this way the depth of penetration can be tuned, thereby affecting linewidth reduction.

The reaction chamber 2 may be constructed and configured to accommodate a single substrate and one of the memory M The program can be programmed with a first period T1 that is between 2 and 6000 times longer than the second period T2, preferably between 4 and 100 times longer, and optimally between 8 and 50 times. The first period T1 of such a reaction chamber may be between 1 and 20000 seconds, preferably between 20 and 4000 seconds, more preferably between 30 and 1000 seconds.

The reaction chamber 2 can be constructed and configured to accommodate 2 to 25 substrates and the program in the memory M can be between 2 to 8000 times longer than the second period T2, preferably between 10 to 500 times and optimally 20 To program the first period T1 between 200 times. The first period T1 of such a reaction chamber may be between 1 and 16000 seconds, preferably between 20 and 7000 seconds, more preferably between 30 and 1500 seconds.

The reaction chamber 2 may be constructed and configured to accommodate 26 to 200 substrates and the program in the memory M may be between 2 and 10,000 times longer than the second period T2, preferably between 10 and 2000 times, more preferably 20 to 1000 times the first time period T1 to program. The first period T1 of such a reaction chamber 2 may be between 1 and 20000 seconds, preferably between 100 and 10000 seconds, more preferably between 200 and 6000 seconds and most preferably between 300 and 4000 seconds between.

In step 54, the second precursor is placed in the reaction chamber 2 by the sequence controller 40 activating the precursor distribution and removal system to place and maintain the second precursor in the reaction chamber for the third period T3. The programming in the memory M can be programmed for a third period T3 of between 1 and 20000 seconds, preferably between 5 and 5000 and optimally between 10 and 2000 seconds.

The memory of the sequencer 40 can be programmed to close the flush valve 24 and the distribution chamber valve 19 and to vaporize the second precursor from the second vessel 31 by opening the second precursor valve 22 and by heating the second vessel 31 Body 29 accumulates the second precursor in the piping of the precursor distribution and removal system upstream of valve 19 in the distribution reaction chamber. The program in the memory M of the sequencer 40 can then be programmed to open the valve 19 for a period of time to release the second precursor 28 is delivered to reaction chamber 2.

The flushing period FP, the loading period LP, and the soaking period SP have been described in conjunction with the first precursor. The memory of the sequencer may be provided with a program which, when executed on the processor of the sequencer 40, will cause the infiltration device to also run the third period T3 having a flushing period FP, a loading period LP and or a soaking period SP . During the entire third time period T3, the second precursor may infiltrate the permeable material and react with the absorbed first precursor derivative in the permeable material, resulting in reinforcement of the permeable material with the infiltrated material.

Optionally, the infiltration cycle may have step 55 in which a portion of the second precursor may be removed for a fourth period of time T4. The sequencer 40 may open the removal chamber valve 36 to remove the second precursor from the reaction chamber 2 with the vacuum pump 38 . Additionally or alternatively, the purge gas 34 may be provided with a purge system to purge the reaction chamber 2 by opening the purge valve 24 and the distribution chamber valve 19 with the sequencer 40 . The fourth period T4 may be between 0.1 and 3000 seconds, preferably between 10 and 500 seconds, more preferably between 30 and 250 seconds and most preferably between 60 and 200 seconds.

Program M can be programmed such that when the program is executed on the processor of the sequence controller 40 of the infiltration device, the infiltration sequence can be repeated in the loop 56 N times, where N is in the range of 1 to 60, preferably 3 to between 20, and optimally between 5 and 12.

Precursors 28 and 29 may be selected such that the precursors form metallic or dielectric infiltrating materials in the infiltrating material. The precursor is vaporized during infiltration and is preferably gaseous.

The first precursor and the second precursor can be used in the apparatus of Fig. 1 to infiltrate the infiltrated material according to the procedure of Figs. 2a and 2b together with: alumina (Al₂O₃), silicon oxide (SiO₂), silicon nitride (SiN), silicon oxynitride (SiON), silicon carbonitride (SiCN), silicon carbide (SiC), titanium carbide (TiC), aluminum nitride (AlN), titanium nitride (TiN), Tantalum Nitride (TaN), Tungsten (W), Cobalt (Co), Oxygen Titanium (TiO)₂), tantalum oxide (Ta₂O₅), zirconia (ZrO₂) or hafnium oxide (HfO₂)。

Alternatively, an infiltrating material, such as a metal or a dielectric, can likewise be deposited on top of the entire volume of infiltrated material with an infiltrating device. For example, if the permeable material is patterned, this can be done to make the pattern wider and more etch resistant.

Patterned structures can be produced using the continuous infiltration synthesis device of FIG. 1 by placing a substrate with patterned infiltrating material on top of reaction chamber 2 and infiltrating the patterned infiltrating material with infiltrating material in at least one infiltration cycle. The patterned permeable material may be a patterned photoresist or DSA material. The substrate may have a hard mask between the substrate and the patterned permeable material. The hard mask can be spin-on glass, spin-on carbon, silicon nitride layers, anti-reflection coatings, amorphous carbon and/or chemical vapor deposition (CVD) layers (eg, SIOC or amorphous carbon layers).

While the substrate remains in the continuous infiltration synthesis device, the infiltrated material can be removed while allowing the infiltrated material to remain on the substrate. The permeable material can be removed by heating the permeable material to a temperature between 80°C and 600°C, preferably 100°C to 400°C and most preferably between 120°C and 300°C. This results in a reduced line width or line width roughness of the patterned structure of the infiltrated material relative to the patterned infiltrated material.

The permeable material can also be removed by setting a plasma to remove the permeable material in the reaction chamber. Plasma containing oxygen or hydrogen can be used to remove a portion of the permeable material and a plasma generator can be utilized to excite oxygen species for efficient removal of the portion of the permeable material. The plasma generator can supply oxygen (O₂) or hydrogen (H₂), or alternatively hydrogen (H₂) or oxygen (O₂) and nitrogen (N₂) gas mixture. The etchant used to remove a portion of the permeable material may thus comprise at least one of an oxygen-excited species and a nitrogen-excited species.

Figure 3 depicts a continuous infiltration device according to another embodiment. Precursor distribution and migration The addition system provides the first or second precursor from one side of the reaction chamber 2 via the inlet port 66 . The inlet port can be closed with valve 19 . The exit port 67 is provided to a distribution and removal system to remove the precursor from the reaction chamber 2 .

The substrate holder 10 for holding the substrate 12 can move up and down. The substrate holder 10 can be moved below the edge 68 of the top of the reaction chamber 2 to allow a substrate handler (not depicted) to set or remove substrates from the substrate holder 10 . By moving it upwards, the reaction chamber can be closed again. The substrate holder 10 may include a third heating member for heating the substrate 12 .

The advantage of the embodiment according to FIG. 3 is that for a single substrate reaction chamber 2, the reaction chamber 2 can have a smaller volume of 0.5-1 liter. The smaller volume makes it possible to have lower precursor usage. The space between the substrate and the top of the reaction chamber may thus be less than 1 cm, preferably less than 5 mm and most preferably less than 3 mm.

Figure 4 depicts a continuous infiltration device according to another embodiment. The reaction chamber 2 contains a showerhead 69 . A showerhead 69 may be provided in the top of the reaction chamber 2 . The showerhead 69 can be connected to the precursor distribution and removal system to provide the first precursor 28 or the second precursor 29 to the surface of the substrate 12 . The precursor distribution and removal system can remove either the first precursor 28 or the second precursor 29 through the opening 67 . A flushing system can also be connected to the showerhead 69 to flush the reaction chamber 2 .

The showerhead 69 may also be connected to a precursor distribution and removal system to remove the first or second precursor from the reaction chamber 2 . In this case, the opening 67 can be connected to a flushing system to flush the reaction chamber 2 .

The substrate holder 10 for holding the substrate 12 can move up and down. The substrate holder 10 may include a third heating member (not shown) for heating the substrate 12 . The advantage of this embodiment is that the showerhead quickly sets up the precursor and removes the precursor from the surface of the substrate while still having an acceptable volume of 2 to 5 liters, preferably 3 to 4 liters.

Figure 5 depicts a continuous infiltration device according to another embodiment. The apparatus comprises a batch reaction chamber 70 of 25 to 250 substrates having a volume of 50 to 200 liters. The substrates can be loaded in a boat 71 provided with substrate holders to accommodate 25 to 250 substrates with the substrate handler. The boat 71 with the substrate can be moved into the reaction chamber 70 in a loading operation by raising the boat into the reaction chamber through an opening at the lower end of the reaction chamber. The bottom portion 71A of the boat 70 can seal the reaction chamber 70 . The heating member 40 may be arranged to control the temperature of the reaction chamber 70 . The first and second precursors can be provided using the inlet 72 and can be removed through the outlet 73 of the precursor distribution and removal system. Valves may be used to control gas flow and care should be taken to ensure that the vaporized precursor is maintained at a temperature above its boiling temperature in reaction chamber 70 . This can be done by having the heating means control the inlet 72 and outlet 73 and up to the temperature of the valve (eg, reaction chamber valve 36).

Where the device is provided with a direct liquid injection system (DLI) comprising a liquid flow controller and an evaporator, the liquid flow controller can control the flow of liquid to the evaporator that evaporates the first or second precursor. It may not be necessary to heat the liquid flowing between the flow controller and the evaporator. The vaporizer may be heated to vaporize the first or second precursor directly.

A vaporizer can be provided in the batch reaction chamber to place the first or second precursor directly in the chamber. Batch reactors make it possible to infiltrate a large number of substrates while increasing the throughput of the device.

High resolution polymer resists can have lower etch resistance and can suffer from higher line edge roughness after exposure. This lower etch resistance and higher line edge roughness can make transfer to the bottom layer more difficult. Therefore, it can be advantageous to infiltrate the patterned resist to change the characteristics of the resist. To perform infiltration, it may be advantageous to have an infiltration device that optimizes the amount of metal infiltrated into the resist.

Accordingly, a continuous infiltration synthesis device is provided, comprising: a reaction chamber 2 (see FIG. 1 ) constructed and configured to hold at least a first substrate 12 provided with a permeable material (eg, a patterned resist); a vaporizer constructed and configured to vaporize hydrocarbon-containing compounds; a second vaporizer constructed and configured to vaporize metal halide-containing compounds; precursor distribution and removal systems 3, 5 constructed and is configured to provide the reaction chamber with a vaporized first precursor from one of the first or second vaporizers and a second precursor from the other of the first and second vaporizers and from the reaction chamber removing the first and second precursors; and a sequencer 40 operatively connected to the precursor distribution and removal system and including a memory M provided with a program that is The infiltration of the permeable material is performed by: activating the precursor distribution and removal system to dispose the first precursor on the permeable material on the substrate in the reaction chamber for a first period of time T1; activating the precursor distribution and removal system removing a portion of the first precursor from the reaction chamber for a second period of time T2; and activating the precursor distribution and removal system to dispose the second precursor on the permeable material on the substrate in the reaction chamber for a third period of time T3 . The first vaporizer may be constructed and configured to vaporize the metal hydrocarbon compound. The second vaporizer can be constructed and configured to vaporize the metal halide compound.

The first and second vaporizers may be part of the precursor distribution and removal systems 3, 5, which may place the first precursor 28 and/or the second precursor 29 in the reaction chamber via the distribution reaction chamber valve 19. The first precursor 28 may be introduced into the chamber 2 as a gas by evaporating the liquid or solid contained in the vessel 30 using the first precursor heater 32 to set a sufficient vapor pressure for delivery into the chamber 2 . The first precursor heater 32 may provide heat to the first precursor in the vessel 30 . Likewise, the second precursor 29 may be introduced into the chamber 2 as a gas by evaporating the liquid or solid contained in the vessel 31 using the second precursor heater 33 to set a sufficient vapor pressure for delivery into the reaction chamber 2 middle.

Following subsequent delivery of the first and second precursors to the reaction chamber 2, the reaction between the permeable material, the metal hydrocarbons and the metal halide ensures that the amount of metal in the permeable metal can be optimized. The amount of metal infiltrated can set the desired etch resistance.

A portion of the first precursor is removed from the reaction chamber for the second period of time T2 between the setting of the first and second precursors may be by, for example, flushing the first precursor with an inert gas (nitrogen) and/or distributing and/or using the precursor and The removal system 3, 5 is done by pumping the first precursor from the reaction chamber. This may be necessary because otherwise the first and second precursors may react on surfaces inside the reaction chamber and form particles and/or contaminants.

The first vaporizer may be constructed and configured to vaporize the aluminum hydrocarbons to metal hydrocarbons. The aluminum hydrocarbon compound may be selected from the group consisting of: trimethylaluminum (TMA), triethylaluminum (TEA), tri-isobutylaluminum (TIBA), tri-tertbutylaluminum (TTBA) dimethyl Ethylaminoalane (DMEAA), dimethylaluminum hydride (DMAH), trimethylaminoalane (TEAA), and N-methylpyrrolidinealane (MPA). The metal hydrocarbon compound may contain nitrogen atoms.

The second vaporizer can be constructed and configured to vaporize metal halide compounds including titanium, hafnium, niobium, and/or zirconium. The halide can be chloride. The metal halide can be selected from the group consisting of: titanium(IV) chloride (TiCl₄), tantalum (V) chloride (TaCl₅), zirconium (IV) chloride (ZrCl₄), hafnium (IV) chloride (HfCl₄) and niobium chloride (NbCl)₅)。

Trimethyl aluminum (TMA) and titanium (IV) chloride (TiCl)₄) penetration can be set at a satisfactory metal concentration in the permeable material, in particular due to the incorporation of titanium (IV) chloride (TiCl₄) can be difficult to fully penetrate into the permeable material.

The program of continuous infiltration into the memory of the synthesis device can be programmed to activate the precursor distribution and removal system to remove at least a portion of the second precursor from the reaction chamber for a fourth period of time T4 after the third period of time T3. A portion of the second precursor is removed from the reaction chamber for a fourth period of time T4 after the second precursor is set up by, for example, flushing the second precursor with an inert gas (nitrogen) and/or using a precursor distribution and removal system to automatically This is done by pumping the second precursor in the reaction chamber. This may be necessary because otherwise the first and second precursors may react and form particles and/or contaminants on the surfaces inside the reaction chamber in subsequent process steps. Removal may be omitted if the second precursor reacts completely without leaving any precursor remaining in the reaction chamber and/or when the remaining first precursor can be allowed to be in the environment of the reaction chamber.

The program that performs the infiltration of the infiltrating material when running on the sequencer can be programmed to repeat at least a portion of the infiltration cycle N times. N can be between 1 and 60, preferably between 1 and 10 and most preferably between 1 and 5 (eg 1, 2, 3 or 4). For example, the entire cycle of setting the first precursor for the first period T1, the first removal for the second period T2, the second precursor for the third period T3 and the second removal for the fourth period T4 may be Repeat N times. Alternatively, a portion of the infiltration cycle may be repeated, such as setting the first precursor for a first period of time T1, a first removal for a second period of time T2, followed by setting the second precursor N times for a third period of time T3 and a second time The removal lasts for the fourth period T4. In this case, the first precursor is only infiltrated once and the second precursor is provided multiple times. But it can also be reversed, where the first precursor is infiltrated multiple times and the second precursor is infiltrated only once.

The continuous infiltration synthesis device can be provided with additional precursor suppliers for providing additional precursors and a precursor distribution and removal system can be constructed and configured to provide reaction chambers with additional precursors from the additional precursor suppliers and to remove additional precursors from the reaction chambers. except for this additional precursor. In the same way that the first precursor 28 can be introduced into the chamber 2 as a gas by evaporating the liquid or solid contained in the vessel 30 using the first precursor heater 32 to set a vapor pressure sufficient for delivery into the chamber 2 In this way, the additional precursor supplier may provide additional precursor to the reaction chamber via the distributed reaction chamber valve 19 in FIG. 1 . The additional precursor supply may thus be provided with additional vessels and additional precursor heaters to set sufficient vapor pressure for additional precursor delivery into chamber 2 . Alternatively, the additional precursor may be provided as a gas so that heating and evaporation is not required.

6 illustrates an infiltration routine that may be performed by the continuous infiltration device of FIG. 1 with an additional precursor supplier system, according to at least one embodiment. In Fig. 6, objects 50 to 56 are the same as the objects with the same numbers in Fig. 2a. The memory M in FIG. 1 may be provided with a program which, when running on the sequential controller, by activating the precursor distribution and removal system at step 57 after the fourth period T4 at step 55 to remove additional precursors The permeable material disposed on the substrate in the reaction chamber continues to infiltrate the permeable material for a fifth period T5. The additional precursor supply may comprise additional containers for storing an oxidant selected from the group comprising: oxygen, water, ozone or hydrogen peroxide. Oxygen (O2) and water can be supplied by supply lines. Ozone (O3) can be generated using the oxygen supply line and ozone generator in the additional precursor supply.

At step 58, the memory may activate the precursor distribution and removal system to remove at least a portion of the additional precursor from the reaction chamber for a sixth period T6. Removal may be omitted if the second precursor reacts completely without leaving any precursor remaining in the reaction chamber and/or when the remaining first precursor can be allowed to be in the environment of the reaction chamber. The latter may be the case if, for example, water, nitrogen or oxygen are used as additional precursors.

The program executing the infiltration of the infiltrating material when running on the sequencer may be programmed to repeat at least a portion of the infiltration cycle N times, also with respect to additional precursors, via 56 . N can be between 1 and 60, preferably between 1 and 10 and most preferably between 1 and 5 (eg 1, 2, 3 or 4). For example, set the first precursor for the first period T1, the first removal for the second period T2, the second precursor for the third period T3, the second removal for the fourth period T4, and the additional The entire cycle of the precursor for the fifth period T5 and the third removal for the sixth period T6 may be repeated N times.

Alternatively, a portion of the infiltration cycle may be repeated, such as setting the first precursor for a first period of time T1, and a first removal for a second period of time T2, followed by setting the second precursor N times for a third period of time T3, a second The second removal lasts for the fourth period T4, the additional precursor is set for the fifth period T5, and the third removal lasts for the sixth period T6. In this case, the first precursor is only infiltrated once and the second and additional precursors are provided multiple times via the selectable shortcut 59 . For example, TMA can be infiltrated once and TiCl₄And water has penetrated many times. It can also be reversed, where the first precursor is infiltrated multiple times and the second and additional precursors are infiltrated only once. Also likewise the first and second precursors can be infiltrated multiple times via the optional shortcut 60 while the additional precursors are infiltrated only once.

The program continuously infiltrated into the memory of the synthesis device may be for a first period T1 between 0.1 and 20000 seconds, a second period T2 between 0.1 and 3000 seconds, and/or a third period between 0.1 and 20000 seconds Time period T3 is programmed. The program of continuous penetration into the memory of the synthesis device can be programmed for a fourth period T4 between 0.1 and 3000 seconds. The fifth time period T5 may be programmed between 0.1 and 20000 seconds. The sixth period T6 may be programmed between 0.1 and 3000 seconds.

The continuous infiltration synthesis apparatus may include a temperature control system constructed and configured to control the temperature of the reaction chamber to a process temperature between 0 and 450°C. A pressure control system in the apparatus can be constructed and configured to control the pressure in the reaction chamber to a process pressure between 0.001 and 1000 Torr.

One or both of the first and second vaporizers may include heaters for heating the first or second precursors. One or both of the first and second vaporizers may comprise a vaporizer for vaporizing the first or second precursor from the liquid. One or both of the first and second vaporizers may include a sublimator for sublimating the first or second precursor from a solid. A buffer volume may be provided between the reaction chamber and at least one of the vaporizers to buffer vaporize the precursor.

<b>Example TMA and TiCl</b>_<b>4</b>

Infiltration in a single wafer reaction chamber of trimethylaluminum (TMA) at a pressure of about 8 Torr can be achieved by infiltrating the first precursor for a duration ranging from 1 to 2000 seconds, preferably 2 to 600 seconds between, more preferably between 4 and 400 seconds, and most preferably between 6 and 200 seconds for the first period T1. At a pressure of about 8 Torr, eg, a program in memory can be programmed to perform a first period T1 of 50 seconds by activating the precursor distribution and removal system to open the first precursor flow path and shut off the gas removing the flow path and placing the first precursor in the reaction chamber for a loading period LP of 30 seconds; and activating the precursor distribution and removal system to close the first precursor flow path and maintain the first precursor in the reaction chamber At the same time the removal flow path was kept closed for a soaking period SP of 20 seconds. It must be understood that these periods are dependent on the (partial) pressure of the first precursor and can be shortened by increasing the pressure, and that they are dependent on the size of the reaction chamber and can be shortened by reducing the size of the reaction chamber.

The second time period T2 may be chosen between 0.01 and 10000 seconds, preferably between 1 and 6000 seconds, more preferably between 5 and 4000 seconds, and most preferably between 20 and 2000 seconds. Removal and/or flushing may be necessary to remove the first precursor from the walls of the reactor in order to be able to render the reaction chamber free of particles. In an optimized reactor, adhesion of the first precursor to the walls can be prevented by other means so that shorter removal/flushing periods are possible. Therefore in this example we use a 4 minute flush, but 20 to 30 seconds is also possible with an optimized system.

Titanium(IV) chloride (TiCl) at a pressure of about 8 Torr₄) in a single wafer chamber by infiltrating the second precursor can last in the range from 1 to 2000, preferably between 2 and 600, more preferably between 4 and 400, and most preferably at A third period T3 between 6 and 200 seconds is completed. At a pressure of about 8 Torr, eg, a program in memory can be programmed to perform a third period T3 of 50 seconds by activating the precursor distribution and removal system to open the second precursor flow path and shut off the gas removing the flow path and placing the second precursor in the reaction chamber for a loading period LP of 30 seconds; and activating the precursor distribution and removal system to close the second precursor flow path and maintain the second precursor in the reaction chamber At the same time the removal flow path was kept closed for a soaking period SP of 20 seconds. It must be understood that these periods are dependent on the (partial) pressure of the second precursor and can be shortened by increasing the pressure, and that they are dependent on the size of the reaction chamber and can be shortened by reducing the size of the reaction chamber.

Figures 7a-7d show Secondary Ion Mass Spectrometry (SIMS) measurements on photoresist layers infiltrated with different infiltration formulations. SIMS is a technique for analyzing the composition of solid surfaces and thin films by sputtering the surface of a sample with a focused primary ion beam, and collecting and analyzing the emitted secondary ions.

Figure 7a depicts the use of 100 sec TMA and 100 sec TiCl₄and no H₂O and N are SIMS measurements on the infiltrated photoresist layer for 5 cycles. Measured weight gain during infiltration is Δm = 2.9 mg/approximately 706 cm²wafer surface. Figure 7a depicts that large amounts of aluminum and titanium have been infiltrated.

Figure 7b depicts the use of 100 s of TMA and 100 s of TiCl₄and no H₂O and N are SIMS measurements on the photoresist layer infiltrated for 1 cycle. Weight gain measured during infiltration is Δm = 1.6 mg/about 706 cm²wafer surface. Figure 7b depicts that a large amount of aluminium and some titanium has been infiltrated.

Figure 7c depicts the use of 100 s of TiCl4 and 100 s of TMA without H₂O and N are SIMS measurements on the photoresist layer infiltrated for 1 cycle. The measured weight gain during infiltration is Δm = 0.92 mg/about 706 cm²wafer surface. Figure 7c depicts that a large amount of aluminium and some titanium has been infiltrated.

Figure 7d depicts the use of 50 s TMA and 20 s H₂O and N are SIMS measurements on a reference photoresist layer penetrated for 1 cycle. The measured weight gain during infiltration was Δm = 0.6 mg/about 706 cm²wafer surface.

As shown in Figures 7a to 7d, under the above process using TMA, a large amount of TiCl was₄Infiltration into permeable materials on the substrate, such as photoresist, may be possible. By first infiltrating TMA and secondly TiCl₄, can achieve higher quality intake. By first infiltrating TiCl₄And secondly, TMA can complete about 30% of lower quality intake. First infiltrate TMA and secondly H₂The mass uptake of O may have a higher ratio than first TMA and second TiCl₄Low about 50% mass gain.

Metal can penetrate uniformly throughout the depth of the permeable layer and when TMA and TiCl are used₄may not appreciably form a skin on the infiltrated material. This may be advantageous if the patterned layer comprising the polymer infiltrates. The patterned layer can then be gently etched with an oxygen plasma. Soft etching can result in some shrinkage of the patterned layer. During the soft etch step, the polymer of the patterned layer may be partially removed, leaving the metal in the layer. Lightly etching the patterned layer can result in some shrinkage of the lines in the patterned layer and can also improve the line edge roughness (LER) of the lines. One or both effects of the soft edge may be desirable.

Figure 8a depicts a similar use of 100 sec TMA and 100 sec TiCl to Figure 7a₄and no H₂O and N are the cross sections of the pattern infiltrated by 5 cycles. The top portion T of Figure 8a shows the pattern before soft etch and the bottom portion B shows the pattern after soft etch. The displayed tie pattern is shrunk a bit, which may be desired.

The continuous infiltration synthesis device can be provided with an additional precursor supply for providing additional precursor (eg, water), and a precursor distribution and removal system can be constructed and configured to provide water to the reaction chamber. Water can cause a skin to form on the permeable material. This may be advantageous if the patterned layer comprising the polymer infiltrates. The patterned layer can then be lightly etched. The soft etch step can result in some shrinkage of the patterned layer. The skin can prevent shrinkage of the patterned layer and correspondingly, if shrinkage is not required, forming the skin with an additional precursor (eg, water) can be beneficial and can also improve the line edge roughness (LER) of the wire by the skin. ).

Figure 8b depicts the use of 100 sec TMA and 100 sec TiCl₄and 20 seconds H₂O and N are the cross sections of the pattern infiltrated by 5 cycles. The top portion T of Figure 8b shows the pattern before soft etching and the bottom B portion shows the pattern after soft etching. It is shown that the pattern does not shrink when additional water precursor is included, which may be desirable.

Additional precursors may be removed from the reaction chamber for a sixth period T6. Removal may be omitted if the additional precursor reacts completely without leaving any precursor remaining in the reaction chamber and/or when the remaining additional precursor can be allowed to be in the environment of the reaction chamber. The latter may be the case if, for example, water is used.

The particular embodiments shown and described are illustrative of the invention and its best mode, and are not intended to otherwise limit the scope of aspects and implementations in any way. Indeed, for the sake of brevity, conventional fabrication, connection, preparation, and other functional aspects of the system may not be described in detail. Furthermore, the connecting lines shown in the various figures are intended to represent exemplary functional relationships and/or physical couplings between the various components. Many alternative or additional functional relationships or entity connections may exist in an actual system, and/or may not exist in some specific instances.

It should be understood that the configurations and/or methods described herein are exemplary in nature and that these particular embodiments or embodiments are not to be considered limiting, as many variations are possible. The particular procedures or methods described herein may represent one or more of any number of processing strategies. Accordingly, the various actions described may be performed in the order described, in other orders, or in some cases omitted.

The subject matter of the present disclosure includes the various processes, systems, and configurations, and other features, acts, acts, and/or characteristics disclosed herein, and all novel and nonobvious combinations and subcombinations of any and all equivalents thereof .