METHOD FOR USING THE SAME

FIELD OF INVENTION

The present disclosure generally relates to apparatus and methods to manufacture electronic devices. More particularly, the disclosure relates to a chemical treatment, deposition and/or infiltration apparatus and method for providing a chemical reaction on and/or in a surface of a substrate using such apparatus.

BACKGROUND

As the trend has pushed semiconductor devices to smaller and smaller sizes, different patterning techniques have arisen. These techniques include spacer defined quadruple patterning, extreme ultraviolet lithography (EUV), and EUV combined 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 patterns for self- assembly. The block copolymers used may include poly(methyl methacrylate) (PMMA), polystyrene, or poly(styrene-block-methyl methacrylate) (PS-b-PMMA). Other block copolymers may include emerging "high-Chi" polymers, which may potentially enable small dimensions.

The patterning techniques described above may utilize an infiltrateable material, such as an EUV polymer or DSA block copolymer resist, disposed on a substrate to enable high resolution patterning of the substrate. To satisfy the requirements of both high resolution and line-edge roughness, the polymer resist may commonly be a thin layer. However, such thin polymer resists layer may have several drawbacks. In particular, high resolution polymer resists may have low etch resistance and may suffer from high line edge roughness. This low etch resistance and the high line edge roughness may makes the transfer of decent patterned to underlying layers more difficult.

It may therefore be advantageous to infiltrate an infiltrateable material, for example the patterned material resist, to alter the properties of the infiltrateable material. To perform infiltration of the patterned material long exposure times to precursors may be necessary. Self-assembled monolayers (SAM) may be used for aiding patterning as well. Self- assembled monolayers of organic molecules may be molecular assemblies formed spontaneously on surfaces by adsorption and self-organization into more or less large ordered domains. Self- assembled monolayers may also require long exposure times to the SAM molecules.

It is therefore advantageously to have an optimized chemical deposition, treatment and/or infiltration apparatus for providing a chemical reaction on and/or in a surface of a substrate.

SUMMARY

In accordance with at least one embodiment of the invention there is provided a chemical treatment, deposition and/or infiltration apparatus for providing a chemical reaction on and/or in a surface of a substrate, wherein the apparatus comprises:

a top and a bottom reaction chamber part forming together a closable reaction chamber; an actuator constructed and arranged for moving the top and bottom reaction chamber parts with respect to each other in at least a first direction from an open position to a closed position to form a closed reaction chamber;

a top substrate holder connected to the top reaction chamber part to hold a substrate at least when the reaction chamber is in the open position; and

a bottom substrate holder connected to the bottom reaction chamber part to hold the substrate when the reaction chamber is in the closed position.

With the top substrate holder connected to the top reaction chamber part and the bottom substrate holder connected to the bottom reaction chamber part closing the reaction chamber by moving the top and bottom reaction chamber parts with respect to each other in at least the first direction may transfer the substrate from the top substrate holder to the bottom substrate holder. By having the top and bottom substrate holders connected to the top and bottom reaction chamber parts respectively and having both reaction chamber parts being moveable with respect to each other there is a simplified design possible without moving parts in the reaction chamber or feedthroughs through the reaction chamber wall for substrate transfer. Such a simplified design may have less leakage of the reaction chamber and therefore may be more precursor efficient.

In accordance with at least one embodiment of the invention there is provided a method for providing a chemical deposition and/or infiltration reaction on and/or in a surface of a substrate with an apparatus comprising a top and a bottom reaction chamber part forming together a closable reaction chamber, the method comprising:

moving the top and bottom reaction chamber parts with respect to each other from a closed position to an open position in a first direction;

moving the substrate in a second direction substantially perpendicular to the first direction above a top substrate holder connected to the top reaction chamber part;

moving the substrate in the first direction onto the top substrate holder;

moving the top and bottom reaction chamber parts with respect to each other in the first direction from an open to a closed position whereby the bottom substrate holder receives the substrate from the top substrate holder;

providing at least a first precursor with the precursor distribution system for chemical reaction on a surface of the substrate.

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

All of these embodiments are intended to be within the scope of the invention herein disclosed. These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of certain embodiments having reference to the attached figures, the invention not being limited to any particular embodiment(s) disclosed.

BRIEF DESCRIPTION OF THE FIGURES

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

Figure 1 depicts a side view on a reaction chamber of a chemical deposition and/or infiltration apparatus according to an embodiment. Figures 2a to 2e depict a substrate loading sequence using the reaction chamber of Figure

1.

Figures 3a to 3d depicts partially a top reaction chamber part usable in the reaction chamber of Figure 1.

Figure 4 depicts a bottom substrate holder usable in the reaction chamber of Figure 1. Figure 5 shows a top view on a chemical deposition and/or infiltration apparatus for implementation of the reaction chamber as described in conjunction with Figures 1 to 4.

DETAILED DESCRIPTION

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

Figure 1 depicts a side view on a reaction chamber 1 of a chemical deposition and/or infiltration apparatus according to an embodiment with all the different parts disconnected for visibility. The apparatus comprises a top and a bottom reaction chamber part 3, 5 forming together a closable reaction chamber 1 made of a suitable material, for example (stainless) steel, titanium, aluminum or quartz. An O-ring 12 may be provided between the top and bottom reaction chamber parts 3, 5 to seal the reaction chamber 1 when the top and bottom reaction chamber parts 3, 5 are moved against each other. A lower section 2 together with a lid 4 which may be joined with an O-ring (not shown) may form the top reaction chamber part 3. A top substrate holder 11 may be provided to the top reaction chamber part 3 to hold a substrate at least when the reaction chamber 1 is in the open position.

The top reaction chamber part 3 may be connected to a precursor distribution system for providing precursors to the reaction chamber. The precursor distribution system may comprises a first and a second precursor delivery inlet 6, 8 for providing precursors to the reaction chamber. The top reaction chamber may be provided with removal system comprising an outlet 10 to remove precursor from the reaction chamber, for example with a pump (not shown).

A bottom substrate holder 13 may be provided to the bottom reaction chamber part 5 to hold the substrate when the reaction chamber 1 is in the closed position. The bottom substrate holder 13 may be provided with a recess 14. The top substrate holder 1 1 may partially move into the recess 14 when the top and bottom reaction chamber parts 3, 5 are moved towards each other to form the reaction chamber 1 during a substrate loading sequence.

Figures 2a to 2e depict a substrate loading sequence using the reaction chamber of Figure 1. Figure 2a depicts a side view on a lower section 2 of a top reaction chamber and a bottom reaction chamber part 5. An actuator 7 may be used for moving the bottom reaction chamber part 5 with respect to the lower section 2 in at least a first direction Z from an open position to a closed position to form a closed reaction chamber or vice versa from a closed position to an open position. The actuator 7 may comprise a piston 16 being moveably mounted in a cylinder 9.

The top substrate holder 11 may be provided to the top reaction chamber part 3 to hold a substrate at least when the reaction chamber 1 is in the open position. Preferably, at least two top substrate holders 11 may be connected to the lower section 2 of the top reaction chamber part at two positions substantially opposite from each other with respect to a center of a substrate to be held by the top substrate holders 11. The top substrate holder 11 may have a clamp 19 with a support area 23 for supporting the substrate and a suspension 21 for suspending the clamp 19 from the lower section 2 of a top reaction chamber part. The support area 23 may be provided with suction or electro static clamping means to hold the substrate 15. The support area 19 may be substantially horizontal and the suspension 21 substantially vertical. The support area 23 may be passive and the substrate may be positioned there by gravity.

A substrate handler, from which the end effector 17 holding the substrate 15 is shown in Figure 2a, may be constructed and arranged for moving the substrate in a second direction X substantially perpendicular to the first direction Z to a position above the top substrate holder 11 when the reaction chamber is in the open position.

Figure 2b depicts an enlarged side view of Figure 2a in which the substrate handler with the end effector 17 holding the substrate 15 on top moved the substrate above the supporting areas 23 of the top substrate holder 11 when the reaction chamber is in the open position. The substrate handler may be moving the substrate 15 in the first direction Z from a position above the top substrate holder 11 to a position on the top substrate holder when the reaction chamber is in the open position. The support area 23 may be provided with suction or electro static clamping means to clamp the substrate 15 on the support area 23 or it may be just be resting there passively by gravity. Figure 2c depicts a view on the configuration of Figure 2b from the bottom in which the end effector 17 of the substrate handler may release the substrate 15 by releasing the suction or electro static force of the end effector 17. The end-effector subsequently moves away from the top substrate holder 1 1 while the substrate 15 remains on the support area 23 of the top substrate holder 1 1.

Figure 2d depicts a view on the configuration of Figure 2c in which the end effector 17 of the substrate handler may move away in the second direction X from the opened reaction chamber. The substrate 15 may remain on the support area 23 of the top substrate holders 1 1.

Figure 2e depicts a side view on the reaction chamber 1 when the substrate handler 17 is moved away out of the reaction chamber space and the reaction chamber 1 is closed by moving the bottom reaction chamber parts 5 towards the lower section 2 of the top reaction chamber part in at least the first direction by the actuator 7. The reaction chamber parts 3, 5 and their respective substrate holders 1 1, 13 are constructed and arranged so that with the movement the substrate will be transferred from the top substrate holder 1 1 to the bottom substrate holder 13 (see Figure 1). The top substrate holder 1 1 may partially move into the recess 14 when the top and bottom reaction chamber parts 3, 5 are moved towards each other to form the reaction chamber 1.

With the top substrate holder 1 1 connected to the top reaction chamber part 3 and the bottom substrate holder 13 connected to the bottom reaction chamber part 5 closing the reaction chamber 1 by moving the top and bottom reaction chamber parts with respect to each other in at least the first direction Z may transfer the substrate from the top substrate holder 1 1 to the bottom substrate holder 13. By having the top and bottom substrate holders 1 1, 13 connected to the top and bottom reaction chamber parts 3, 5 respectively and having both reaction chamber parts being moveable with respect to each other there is a simplified design possible without moving parts in the reaction chamber 1 or feedthroughs through the reaction chamber wall.

Such a design may have less leakage of the reaction chamber 1 and therefore may be more precursor efficient. The latter is especially important for infiltration, treatment and/or deposition processes with longer exposure times to precursors.

For example, in case the pressure in the reaction chamber is different than the pressure outside the reaction chamber 1 the pressure difference may be retained between 50 to 100%, preferably 75 to 100%, more preferably 90 to 100%, even more preferably 95 to 100%, and most preferable 98 to 100% from the original pressure difference for longer than 30 seconds, preferably longer than 1 minute, more preferably longer than 2 minutes, even more preferably longer than 5 minutes, and most preferably longer than 10 minutes without supplying/exhausting gases.

The reaction chamber 1 may have a He leak rate of less than about 10-3 mbar * 1/s, preferably less than about 10-5 mbar * 1/s, more preferably less than about 10-6 mbar * 1/s, even more preferably less than about 10-7 mbar * 1/s and most preferably less than about 10-8 mbar * 1/s.

The top reaction chamber part 3 may be stationary while the bottom reaction chamber part 5 may be moveable up and down in the first direction Z with the actuator 7. In this configuration the precursor distribution system for providing precursors to the reaction chamber and the removal system to remove precursor from the reaction chamber may be operable connected with rigid tubing to the top reaction chamber part because the tubing doesn't need to provide flexibility for movement of the top reaction chamber part 3. The precursor distribution system and/or the removal system may employ a purging system to provide for purging of the reaction chamber.

Figure 3a depicts a lower section 2 of the top reaction chamber part 3 with the top substrate holder 11 protruding from the lower section 2 of top reaction chamber part 3 in the direction of the bottom reaction chamber part 5. The lower section 2 together with a lid (not shown) which may be joined with an O-ring there in between are part of the top reaction chamber part 3.

Figure 3b depicts the two top substrate holders 11 to be constructed and arranged in an U- shape seen in the first direction from the top. The open end of the U may be configured in the apparatus in the direction of the center of the substrate when positioned on the top substrate holder. The two top substrate holders may be constructed and arranged to have the support area 23 (see Figure 3c) at the top of the U while the suspension 21 may be mounted at the bottom of the U. The bottom of the U may substantially follow the circle shape of the substrate to be positioned on the top substrate holder. In this way four support areas 23 of the top substrate holders 11 may support the substrate. The support area 23 may be less than 50 mm preferably around 30 mm long and less than 30 mm preferably around 20 mm wide. Figure 3c depicts the two top substrate holder 11 constructed and arranged to have a L- shape seen in the second direction which is perpendicular to the first direction and is parallel to the direction in which the substrate handler is moving the substrate in between the top substrate holders 11. The lower end of the L may be configured in the apparatus to point in the direction perpendicular to the first and second direction. The two top substrate holders 11 may be constructed and arranged to have the clamp 19 at the lower end of the L while the suspension 21 may be at the top of the L. The height of the suspension 21 defines the space which the substrate handler has for moving the substrate above the clamps 19 of the top substrate holder 11. The height of the suspension 21 may be less than 20 mm, preferably less than 10 mm, for example around 6 mm. The height of the clamps 19 may be less than 10 mm, preferably around 6 mm to provide sufficient strength within the top substrate holder 11.

Figure 3d depicts the two top substrate holder 11 constructed and arranged to have an upside down T-shape seen in a direction perpendicular to the first and second direction. The two top substrate holders may be constructed and arranged to have the clamps 19 at the top end of the T while the suspension 21 may be at the lower end of the T.

Figure 4 depicts the bottom substrate holder 13 provided with a recess 14 in its top flat surface 29. The clamp 19 of the top substrate holder 11 (in Fig. 2) may move into the recess 14 when the top and bottom reaction chamber parts 3, 5 are moved in the first direction to form the reaction chamber. With the movement of the clamp 19 into the recess 14 the substrate is transferred from the top substrate holder 11 to the bottom substrate holder 13. The recess may have a depth a little larger than the thickness of the clamp, e.g., less than 2 cm, preferably less than 1 cm and most preferably less than 7 mm but more than 0.5 mm, preferably more than 1 mm and more preferably more than 3 mm.

The space between substrate and the top of the reaction chamber 1 may be less than 5 cm, preferably less than 3cm, more preferably less than 2 cm, even more preferably less than 1 centimeter, even more preferably less than 5 mm and most preferably less than 3 mm but more than 0.5 mm, preferably more than 1 mm. In this way the volume of the reaction chamber can be minimized which is advantageous for precursor consumption. The volume of the reaction chamber 1 for substrates having a 300 mm diameter may be less than about 20 liters, preferably less than about 10 liters, less than about 5 liters, less than about 2 liters and less than about 1 liters but more than 0.1 liters, preferably more than 0.5 liters. The flat surface 29 of the bottom substrate holder 13 is for receiving the substrate when the top substrate holders are moving into the recess 14. The bottom substrate holderl3 may be provided with suction or electro static clamping means to hold the substrate on the flat surface 29 or the substrate may just lay there passively. The bottom substrate holder may be provided with a heater for heating the substrate via the flat surface 29. To provide for uniform heating the flat surface may have the same size as the substrate and the recess should be made small. Advantageously, the distance between the top substrate holder 11 and the edge of the recess 14 may be made very small in the order of a few millimeter. The top reaction chamber part comprising the lower section 2 and the lid may also be provided with a heater for heating the reaction chamber.

The substrate may be fully supported by the bottom substrate holder 13 when the reaction chamber is closed or alternatively a part of the substrate may be still be partially supported by the top substrate holder. In the latter case the supporting area of the top support holder may be provided with a heater to improve uniform heating of the substrate.

The apparatus is "pinless," which means that there are no lift pins to receive the substrate from the substrate handler and to lower the substrate on the bottom substrate holder. The lift pins would require a hole through the reaction chamber for their movement which would be disadvantageous because it may cause a leakage. The apparatus may not have holes to the outside environment of the reaction chamber, therefore it may be more easy to retain the pressure in the reaction chamber 1. The lift pins may also cause problems such as sticking of movable parts which may be avoided in a "pinless" design.

In some embodiments the top and bottom reaction chamber parts forming together the closable reaction chamber 1 have no machined structures (e.g., holes) which would allow gases to pass through the reaction chamber parts and which later on in the fabrication process may be closed. This reduces the risk of leakage and may also make the uniformity of the heating better, for example, by circumventing cold spots.

Figure 5 shows a top view on a chemical deposition and/or infiltration apparatus according to an embodiment. The apparatus according to Figure 5 may use the reaction chamber as described in conjunction with Figures 1 to 4.

Shown are cassette loading stations 31 for loading cassettes (e.g., Front Opening Unified

Pod's FOUP) with multiple substrates. A front substrate handler 33 may be used to move the substrates from the cassettes to an intermediate loading station. The intermediate loading station may be a loadlock 35. Subsequently, a substrate handler 37 may be used to move the substrates 15 from the intermediate loading station to the reaction chambers 1 provided with the top and bottom substrate holders.

All reaction chambers 1 may be accessible by the substrate handler 37 for a single substrate 15 at the time. Four substrates can be processed simultaneously in four reaction chambers. The substrate handler 37 may be moveable in the Z direction and may have an end effector 17 shown in Figures 2b to 2d to hold and drop the substrate on the top substrate holder 11.

The apparatus may comprises a sequence controller 39 for controlling the precursor distribution and removal systems 43 and provided with a memory 41 being programmed to enable the apparatus to execute deposition and/or infiltration. The program in the memory may control the apparatus to deposit and/or infiltrate in at least a first cycle comprising:

providing a first precursor in the reaction chamber by the precursor distribution system for a first duration via the first precursor delivery inlet 22 (see Figure 1) for providing precursors to the reaction chamber 1;

removing a portion of the first precursor from the substrate for at least a second duration by the removal system via outlet 26 to remove precursor from the reaction chamber;

providing a second precursor in the reaction chamber by activating the precursor distribution system to provide the second precursor for a third duration in the reaction chamber via the second precursor delivery inlet 24 for providing precursors to the reaction chamber.

The sequence controller 39 may be programmed to leave the first or second precursor in the reaction chamber while having the precursor distribution and removal systems 43 deactivated for a soak period after providing the first precursor in the reaction chamber. In this way there is no usage of first or second precursor while the first precursor is just remaining stationary in the reaction chamber while absorbing, reacting and/or infiltrating.

The substrate handler 37 may be positioned in a chamber from which the air will be removed with a removal system and the substrate handler 37 may be receiving substrates from a load lock 35. Substrates may be positioned in the load lock. The air in the load lock may be removed and the door to the substrate handler 37 may open so that the substrate handler may move the substrate from the load lock to the reaction chamber 1. Operating the apparatus in this way may make it possible to control the interior of reaction chamber 1 to be extremely clean.

The precursor distribution system may provide a first or a second precursor to the reaction chamber 1 via the first and second precursor inlet 22, 24 (see Figure 1). The first precursor may be introduced as a gas into the chamber by evaporating a liquid or solid contained in a container by a first precursor heater to provide adequate vapor pressure for delivery into the chamber. The first precursor heater may provide heat to the first precursor in the container. Equally a second precursor may be introduced as a gas into the chamber by evaporating a liquid or solid contained in container by a second precursor heater to provide adequate vapor pressure for delivery into the reaction chamber.

The precursor distribution and removal systems 43 may comprise a purge system to provide a purge gas to the reaction chamber via a purge valve. The purge gas may be an inert gas such as nitrogen or helium and may be used to purge the reaction chamber.

The precursor may be a compound having an element of the infiltration material or deposition layer to be formed on the substrate. The precursor may be the self-assembled monolayers (SAM) molecule which for example may be used for passivation of surfaces in selective deposition and maybe therefore be aiding patterning.

The temperature of the reactor 1 may be between 50 and 250°C, more preferably 100 and

200°C and most preferably 130 and 170°C during deposition of SAMs. The pressure of the reactor 1 may be between 0.01 and 10 Torr, preferably between 0.05 to 2 Torr and most preferably between 0.1 to 1 Torr during deposition of SAMs. The duration of the reaction may be between 1 to 60, preferably 5 to 30 and most preferably 8 to 15 minutes.

The precursor may be provided into the reaction chamber through first precursor valve and the first precursor inlet. The precursors may be stored in containers and may be replaced with other suitable precursor storage means if required. For example, if one of the precursors may be solid there may be provided specially adapted containers to accelerate sublimation of the solid precursor. One of the containers may also be provided with a gaseous precursor such that heating is not required.

The sequence controller 39, e.g., a microcontroller, may be operably connected to the one or more precursor valves and a purge valve and the removal system. The sequence controller 39 may comprise a memory 41 to store a program being programmed to enable the apparatus to execute infiltration of the infiltrateable material provided on the substrate in the reaction chamber with the first and second precursor. A pressure and/or temperature sensor may monitor the chamber pressure and temperature and may be operably connected with the sequence controller during operation to optimize the process conditions of the infiltration.

The program stored in the memory 41 of the sequence controller 39 may be programmed to sequence the opening and closing of the valves at the appropriate times to provide and remove the first and second precursor to the reaction chamber. The precursor valves may be heated.

The apparatus may be provided with a heating system comprising a first heating element, e.g., a heating resistor wire and a heating controller operably connected to temperature sensors. A pressure sensor may be provided as well. The heating controller may be operably connected to the sequence controller 39. The temperature sensors may be used to measure the temperature in the reaction chamber and provide feedback to the heating controller about this temperature to adjust the temperature of the heating element to adjust the temperature of the reaction chamber.

For example if the first or second precursor is trimethylaluminium (TMA) the vapor pressure is:

20°C ~ 9 Torr

40°C ~ 25Torr

60°C ~ 64 Torr

80°C ~ 149 Torr

100°C ~ 313 Torr

128°C ~760Torr

As can be seen from these values the processing pressure can be increased substantially by increasing the temperature in the reaction chamber. However if there is a small portion in the apparatus which is in contact with the precursor and which has a slightly lower temperature there is an immediate risk of condensation of the precursor which is unwanted.

The interaction of a precursor, e.g., TMA with the infiltrateable material or the substrate may be primarily through adsorption and diffusion. The temperature may have a significant effect on the infiltration because the rate of adsorption and diffusion and the equilibrium in an adsorption reaction may be impacted by changes in temperature.

The infiltration process may be optimal at 90°C, while at 120°C and 150°C, the infiltration is less good for TMA. This may be expected for an adsorption based process. At higher temperature the equilibrium of the adsorption reaction may shift towards separate TMA and polymer species. A process temperature between 20 and 400, preferably between 50 and 150, more preferably between 60 and 110 and most preferably between 65 and 95°C is therefore preferred.

The heating system may therefore be constructed and arranged to control the temperature of the reaction chamber and a duct from the reaction chamber up to at least their respective reaction chamber valves to between 20 and 450, preferably between 50 and 150, more preferably between 60 and 110 and most preferably between 65 and 95°C. The memory 41 in the sequence controller 39 may be programmed with a program for the apparatus to reach and/or maintain a pressure of the first or second precursor in the reaction chamber between 0.001 and 1000 Torr, preferably between 0.1 and 400 Torr, more preferably between 1 and 100 Torr and most preferably between 2 and 50 Torr during infiltration to avoid condensation. In this way we create a sufficient safety margin to avoid condensation in the apparatus while having an optimum process temperature and pressure with respect to the use of the precursor TMA.

The apparatus may comprise a direct liquid injector (DLI) comprising a liquid flow controller and a vaporizer. The liquid flow controller may control a liquid flow to an vaporizer to evaporate the first or second precursor. There may not be a need to heat the liquid flow between the flow controller and the vaporizer. The vaporizer may be heated to evaporate the first or second precursor. The heating system may be constructed and arranged to control the temperature from the reaction chamber up to the vaporizer to at least a boiling temperature of the first or second precursor at the pressure of the first or second precursor in the reaction chamber to avoid condensation. The vaporizer may be constructed and arranged in the reaction chamber to directly provide the evaporated precursors in the reaction chamber. The vaporizer may also be constructed and arranged in the precursor distribution and removal system of the apparatus.

The heating system, e.g., heating elements may be a resistor wire being wound around the relevant portions of the apparatus or provided in the bottom substrate holder. The heating elements may be multizone heating elements with multiple temperature sensors to control the temperature in every part of the tool more precisely.

The precursor distribution and removal system may comprise a bubbler for providing the precursor. The bubbler may provide a non-continuous precursor flow having pulses of the first precursor of 0.1 to 200, preferably 1 to 3 seconds alternating with pulses of a mixing gas for 0.01 to 2, preferably 0.3 to 1 seconds.

The precursor distribution and removal system may be provided with a direct liquid injector (DLI) vaporizer to directly inject the gaseous precursor in the reaction chamber or in other duct of the precursor distribution and system.

During a typical infiltration operation, the first precursor may be infiltrated in the infiltrateable material on the substrate by exposure to the first precursor in vapor phase from the container. The first precursor may react with the infiltrateable material on the substrate and become a chemi-sorbed or physi-sorbed derivative infiltrated in the infiltrateable material on the substrate. Subsequently the second precursor may be infiltrated in the infiltrateable material on the substrate by exposure to the second precursor in vapor phase from the container. The second precursor may react with the chemi-sorbed or physi-sorbed derivative of the first precursor infiltrated in the infiltrateable material on the substrate to become the final infiltration material.

The containers for storing a first or second precursor may be constructed and arranged to store an alkyl compound of aluminum selected from the group consisting of trimethyl aluminum (TMA), triethyl aluminum (TEA), and dimethylaluminumhydride (DMAH). The containers may be constructed and arranged to store a first or second precursor such as titanium(IV)chloride (TiCl), tantalum(V)chloride (TaC15), and/or niobium chloride (NbC15).

For infiltrating zirconium or hafnium the containers may be constructed and arranged to store a Zr or Hf precursor. The Zr or Hf precursor may comprise metalorganic, organometallic or halide precursor. In some embodiments the precursor is a halide. In some other embodiments the precursor is alkylamine compound of Hf or Zr, such as TEMAZ or TEMAH.

The containers may be constructed and arranged to store a first or second precursor such as an oxidant chosen from the group comprising water, ozone, hydrogen peroxide, ammonia and hydrazine.

The apparatus may comprise a first container for containing the first or second precursor such as an aluminum or boron hydrocarbon compound preferably selected from the group consisting of trimethyl aluminum (TMA), triethyl aluminum (TEA), dimethylaluminumhydride (DMAH) dimethylethylaminealane (DMEAA), trimethylaminealane (TEAA), N- methylpyrroridinealane (MPA), tri-isobutylaluminum (TIBA), tritertbutylaluminum (TTBA) trimethylboron and triethylboron and a second container for containing the other of the first and second precursor such as a metal halide preferable from the group consisting of titanium(IV)chloride (TiCl), tantalum(V)chloride (TaC15), and niobium chloride (NbC15). The latter may be preferable for infiltrating metal carbide material.

The infiltrateable material may be porous. Porosity may be measured by measuring the void spaces in the infiltrateable material as a fraction of the total volume of the infiltrateable material and may have a value between 0 and 1. The infiltrateable material may be qualified as porous if the fraction of void spaces over the total volume is larger than 0.1, larger than 0.2 or even larger than 0.3.

In an embodiment the infiltrateable material may be a patterned layer for example a patterned (photo)resist layer. The resist layer may be annealed. The anneal step may have a purpose of degassing moisture or other contaminants from the resist, hardening the resist, selectively burning away portions of the resist from the substrate surface or creating the required porosity.

In an embodiment the patterned layer may be provided by having a block copolymer film and promoting directed self-assembly of the block copolymer film to form the patterned layer. Infiltrating such patterned layer may improve the quality of such patterned layer. The block copolymer film may, for example, have a low etch resistance and by infiltrating the pattern in the copolymer the etch resistance of the pattern may be improved.

In an embodiment the patterned layer may be provided by having a photoresist being exposed with a lithographic apparatus. Infiltrating such patterned layer may improve the quality of such patterned layer. The patterned photoresist layer may, for example, have a low etch resistance and by infiltrating the patterned photoresist the etch resistance of the pattern may be improved.

After the substrate is positioned in the reaction chamber in Figure 1 the reaction chamber and substrate may be cleaned by the removal pump evacuating the reaction chamber. Optionally a purge gas may be provided with the purge system to flush the reaction chamber via the purge valve. The reaction chamber may be heated to enhance outgassing.

The program in the memory 41 may be programmed to activate the precursor distribution and removal system 43 to remove gas from the reaction chamber and to provide purge gas with the purge system to have the reaction chamber purged for 1 to 4000 seconds, preferably 100 to 2000 seconds before the infiltration is started. The program in the memory may be programmed to activate the heater system to heat the reaction chamber to a temperature between 20 and 450°C, preferably between 50 and 150°C and most preferably between 70 and 100°C to enhance outgassing of contaminants.

Subsequently, the method comprises an infiltration method in which the infiltrateable material may be infiltrated with the infiltration material during one or more infiltration cycles. Each infiltration cycle may comprise the following steps:

Providing a first precursor to the substrate in the reaction chamber for a first period. The memory 41 of the sequence controller 39 may be provided with a program which when executed on the processor of the sequence controller 39 makes the apparatus close the purging valve and to deliver the first precursor to the reaction chamber 1 via inlet 22.

This may be done with the outlet 26 opened and the removal pump activated for a flush period FP to flush the reaction chamber 1 with the first precursor. The flush period FP may also be omitted. The program in the memory 41 may be programmed to activate the first precursor flow controller for the flush period FP between 1 to 60, preferably between 2 and 30 seconds.

The first precursor may also be provided to the reactor chamber 1 with the precursor distribution and removal system 43 while not removing any precursor with the removal system for a load period LP. This results in a pressure buildup of the first precursor in the reaction chamber 1. This build up may be terminated by the sequence controller 39 when the pressure of the first or second precursor in the reaction chamber 1 reaches a maximum desired pressure. Alternatively, there may be a pressure release valve which opens when the pressure in the reaction chamber increases above a predetermined maximum which may also end the pressure load period LP. The program in the memory 41 may be programmed to activate the first precursor flow controller for the load period LP between 1 to 3000, preferably between 3 and 1000, more preferably between 5 to 500 seconds.

The first precursor may be maintained residing stationary in the reaction chamber 1 while having the precursor distribution and removal system 43 not providing or removing any precursor for a soak period SP. The program in the memory 41 may be programmed to activate the first precursor flow controller for a soak period SP between 10 to 9000, preferably between 50 and 5000 seconds and more preferably between 100 and 1000 seconds.

The first period Tl therefore may comprise a flush period FP, a load period LP, and/or a soak period SP. During the whole period Tl the first precursor may infiltrate and/or absorb. The memory 41 of the sequence controller 39 may be programmed with the program when executed on a processor of the sequence controller making the apparatus to provide and maintain the first precursor for the first period Tl between 1 to 20000, preferably between 20 to 6000, more preferably between 50 and 4000, and most preferably between 100 and 2000 seconds in the reaction chamber.

A portion of the first precursor may be removed for a second period T2. The sequence controller 39 may control the removal system to remove the first precursor from the reaction chamber 1 via the outlet 26. Additionally, a purge gas may be provided with the purge system to flush the reaction chamber 1.

The program in the memory 41 of the sequence flow controller 39 may be programmed with a program when executed on a processor of the sequence controller 39 makes the apparatus to control the second duration T2 of removing the portion of the first precursor. The program in the memory 41 may be programmed with the second period T2 between 0.1 to 20, preferably between 0.5 to 10 seconds.

The second precursor may be provided in the reaction chamber 1 by the sequence controller 39 activating the precursor distribution and removal system 43 to provide and maintain the second precursor for a third duration T3 in the reaction chamber. The memory 41 of the sequence controller 39 may be programmed to deliver the second precursor to the reaction chamber 1.

The flush period FP, load period LP, and soak period SP have been described in conjunction with the first precursor. The memory 41 of the sequence controller 39 may be provided with a program when executed on the processor of the sequence controller 39 will make the apparatus run the third period T3 with a flush period FP, a load period LP, and/or a soak period SP of the second precursor. During the whole third period T3 the second precursor may react with the absorbed first precursor derivative.

Optionally, a portion of the second precursor may be removed for a fourth period T4. The sequence controller 39 may activate the removal system to remove second precursor with the vacuum pump 38 from the reaction chamber 1. Additionally a purge gas may be provided with the purge system to flush the reaction chamber 1. The program in the memory 41 may be programmed with the fourth period T2 between 0.1 to 100, preferably between 0.5 to 20 seconds. The memory 41 of the sequence controller 39 may be programed so that when the program is executed on a processor of the sequence controller 39 of the apparatus the infiltration sequence may be repeated N times, wherein N is between 1 to 20, preferably 2 to 10 and most preferably between 3 to 6. The precursors may be chosen such that the precursors form a metal or dielectric infiltration material.

The first precursor and the second precursor may be utilized together in the apparatus of Figure 1 to produce aluminum oxide (A1203), silicon oxide, (Si02), silicon nitride (SiN), silicon oxynitride (SiON), silicon carbonitride (SiCN), silicon carbide (SiC), titanium carbide (TiC), aluminum nitride (A1N), titanium nitride (TiN), tantalum nitride (TaN), tungsten (W), cobalt (Co), titanium oxide (Ti02), tantalum oxide (Ta205), zirconium oxide (Zr02), or hafnium oxide (Hf02).

A process temperature between 20 and 400, preferably between 50 and 200, more preferably between 60 and 150°C and a pressure of the first or second precursor in the reaction chamber between 0.001 and 1000 Torr, preferably between 0.05 and 100 Torr, and more preferably between 0.1 and 10 Torr to avoid condensation may also be preferred for deposition of layers.

The particular implementations shown and described are illustrative of the invention and its best mode and are not intended to otherwise limit the scope of the aspects and implementations in any way. Indeed, for the sake of brevity, conventional manufacturing, 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 elements. Many alternative or additional functional relationship or physical connections may be present in the practical system, and/or may be absent in some embodiments.

It is to be understood that the configurations and/or approaches described herein are exemplary in nature, and that these specific embodiments or examples are not to be considered in a limiting sense, because numerous variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Thus, the various acts illustrated may be performed in the sequence illustrated, in other sequences, or omitted in some cases. The subject matter of the present disclosure includes all novel and nonobvious combinations and sub-combinations of the various processes, apparatus, systems, and configurations, and other features, functions, acts, and/or properties disclosed herein, as well as any and all equivalents thereof.