TW201728778A - Low vapor pressure aerosol-assisted CVD - Google Patents

Abstract

Systems and methods for processing films on the surface of a substrate are described. The systems possess aerosol generators which form droplets from a condensed matter (liquid or solid) of one or more precursors. A carrier gas is flowed through the condensed matter and push the droplets toward a substrate placed in a substrate processing region. An inline pump connected with the aerosol generator can also be used to push the droplets towards the substrate. A direct current (DC) electric field is applied between two conducting plates configured to pass the droplets in-between. The size of the droplets is desirably reduced by application of the DC electric field. After passing through the DC electric field, the droplets pass into the substrate processing region and chemically react with the substrate to deposit or etch films.

Description

Low vapor pressure aerosol assisted chemical vapor deposition

Embodiments described herein relate to chemical vapor deposition using a low vapor pressure precursor.

Forming a thin film on a substrate by chemical reaction of a gas is one of the main steps in the manufacturing process of modern semiconductor devices. These deposition processes include chemical vapor deposition (CVD) and plasma enhanced chemical vapor deposition (PECVD), which are combined with conventional CVD techniques using plasma. CVD and PECVD dielectric layers can be used as different layers in a semiconductor component. For example, the dielectric layer can be used as a dielectric layer between the conductive lines or interconnects in the component. Alternatively, the dielectric layer can be used as a barrier layer, an etch stop layer or spacer, as well as other layers.

Chemical precursors have been introduced into the substrate processing region of the substrate processing chamber. The substrate is positioned within the substrate processing region and one or more precursors can be introduced into the substrate processing region to deposit a thin film. The liquid precursor can be used by passing the carrier gas through the liquid in a "foaming" manner to carry the vapor into the substrate processing zone. The effectiveness of this technique depends on the vapor pressure of the liquid. The temperature of the liquid can be increased to increase the vapor pressure. Ultrasonic generators have also been used to generate droplets to increase delivery of precursors to the substrate processing region, however, droplet size can adversely affect deposition uniformity and gap fill capability.

There is a need for a method for reducing droplet size in aerosol-assisted CVD to broaden the available applications in which low vapor pressure precursors can be utilized.

Systems and methods are described for processing a film on a surface of a substrate. The system has an aerosol generator that forms droplets from a condensed substance (liquid or solid) of one or more precursors. The carrier gas flows through the condensed material and pushes the droplets toward the substrate placed in the substrate processing region. An inline mechanical pump coupled to the aerosol generator can also be used to push the droplets toward the substrate. A direct current (DC) electric field is applied between two electrically conductive sheets that are configured to pass the droplets between the two electrically conductive sheets. The size of the droplets is reduced as needed by the application of the DC electric field. After passing through the DC electric field, the droplets enter the substrate processing region and chemically react with the substrate to deposit or etch a thin film.

Embodiments described herein include apparatus for forming a self-assembled monolayer on a substrate. The device includes a heated carrier gas source. The apparatus further includes an aerosol generator configured to receive a heated carrier gas from the heated carrier gas source and configured to generate aerosol droplets from the condensate precursor. The device further includes a precursor conduit configured to receive the aerosol droplets. The device further includes a DC power source. The device further includes a top electrode and a bottom electrode. The top electrode and the bottom electrode are parallel and form an electrical gap configured to receive the aerosol droplets. The top electrode and the bottom electrode are biased with a differential voltage from the DC power source by means of a vacuum electrical feedthrough. The differential voltage is applied between the top electrode and the bottom electrode to reduce the size of the aerosol droplets. The device further includes a substrate pedestal disposed within the substrate processing region within the chamber. The substrate pedestal is configured to support the substrate during formation of the self-assembled monolayer.

The differential voltage can be selected to form an electric field having a magnitude between 500 V/cm and 20000 V/cm. The differential voltage can be between 100 volts and 2 kilovolts. The aerosol droplets may have a diameter between 3 nm and 75 nm.

Embodiments disclosed herein include a substrate processing apparatus. The substrate processing apparatus includes a substrate pedestal disposed in a substrate processing region within the substrate processing apparatus. The substrate pedestal is configured to support the substrate during processing of the film. The substrate processing apparatus further includes a carrier gas source. The substrate processing apparatus further includes an aerosol generator configured to receive a carrier gas from the carrier gas source and configured to generate aerosol droplets from the liquid precursor. The substrate processing apparatus further includes a heater for heating the carrier gas between the carrier gas source and the aerosol generator. The substrate processing apparatus further includes a piezoelectric transducer that is attached to the aerosol generator to facilitate the generation of the aerosol droplets. The substrate processing apparatus further includes a precursor conduit configured to receive the aerosol droplets. The substrate processing apparatus further includes a DC power source. The substrate processing apparatus further includes a first electrode and a second electrode. The first electrode and the second electrode are parallel to each other and separated by a gap. The gap is configured to receive the aerosol droplets and receive a voltage from the DC power source via a vacuum electrical feedthrough. The voltage is applied between the first electrode and the second electrode to reduce the size of the aerosol droplet to an aerosol droplet size between 3 nm and 75 nm and to The size of the aerosol droplets is maintained between 3 nm and 75 nm until the aerosol droplets reach the substrate.

The liquid precursor may include octyl phosphate (CH ₃ (CH ₂ ) ₆ CH ₂ -P(O)(OH) ₂ ), perfluorinated octyl phosphate (CF ₃ (CF ₂ ) ₅ CH ₂ -CH ₂ -P(O)(OH) ₂ ), octadecylphosphonic acid (CH ₃ (CH ₂ ) ₁₆ CH ₂ -P(O)(OH) ₂ ), decylphosphonic acid, tricresylphosphonic acid, ring One or more of hexylphosphonic acid, hexylphosphonic acid or butylphosphonic acid. The first electrode and the second electrode may be of a level. The substrate can be parallel to both the first electrode and the second electrode. The substrate may be disposed between the first electrode and the second electrode. The piezoelectric transducer can be in direct contact with the liquid precursor. The liquid precursor can be formed by dissolving a solid precursor in a solvent. The substrate may be perpendicular to both the first electrode and the second electrode. The substrate base can be an electrical insulator.

Embodiments disclosed herein include a substrate processing chamber for forming a thin film on a substrate. The substrate processing chamber includes a carrier gas source. The substrate processing chamber further includes an aerosol generator configured to receive a heated carrier gas from a heated carrier gas source and configured to generate aerosol droplets from the condensate precursor. The substrate processing chamber further includes a precursor conduit configured to receive the aerosol droplets. The substrate processing chamber further includes a DC power source. The substrate processing chamber further includes a first electrode and a second electrode, the first and second electrodes being configured to receive a DC voltage from a DC power source. The first electrode and the second electrode are parallel, and a gap is formed between the first electrode and the second electrode. The DC voltage is applied between the first electrode and the second electrode to reduce the size of the aerosol droplets. The DC voltage applied between the first electrode and the second electrode forms an electric field that is directed from the first electrode directly to the substrate and directly to the second electrode. The substrate processing chamber further includes a substrate pedestal disposed within a substrate processing region within the chamber. The substrate pedestal is configured to support the substrate during processing of the film.

The gap can be configured to receive the aerosol droplets directly from the precursor conduit without passing the aerosol droplets through the first electrode or the second electrode. The gap can be configured to receive the aerosol droplets through one or more of the first electrode or the second electrode. The substrate base may include a carbon block.

Embodiments of the invention include methods of forming a layer on a substrate. The method includes placing the substrate into a substrate processing region of a substrate processing chamber. The method further includes placing the liquid precursor into an aerosol generator. The method further includes passing a carrier gas stream into the aerosol generator for generating aerosol droplets. The method further includes applying an electric field to the aerosol droplets. The method further includes flowing the aerosol droplets into the substrate processing region. The method further includes forming the layer from the aerosol droplets on the substrate.

The layer can be one of a Group II-VI or a Group III-V semiconductor. The layer may be one of boron nitride, aluminum nitride, gallium arsenide, gallium phosphide, indium arsenide or indium antimonide. The layer may be a metal oxide or may be composed of oxygen and a metal element. The electric field can be a DC electric field having an electric field directed to the substrate. The method can further include flowing a second precursor into the substrate processing region to form a single layer on the layer. The electron temperature in the substrate processing region during the formation of the layer may be less than 0.5 eV.

Embodiments of the invention include methods of processing layers on a substrate. The method includes placing the substrate into a substrate processing region of a substrate processing chamber. The method further includes dissolving the solid precursor in a solvent to form a precursor solution within the aerosol generator. The method further includes passing a carrier gas stream into the aerosol generator for generating aerosol droplets. The method further includes applying an electric field to the aerosol droplets. The method further includes flowing the aerosol droplets into the substrate processing region. The method further includes etching a layer on the substrate by chemical reaction with the aerosol droplets.

The layer may consist of only two elements. The layer may be composed of a group III element and a group V element. The layer may consist of a Group II element and a Group VI element. The method can further include flowing a second precursor into the substrate processing region to remove a single layer from the layer. The electric field can be a DC electric field having an electric field directed to the substrate. The electric field can have a magnitude between 500 V/cm and 20,000 V/cm. The aerosol droplets may have a diameter between 3 nm and 75 nm. The temperature of the electrons in the substrate processing region during etching of the layer may be less than 0.5 eV.

Additional embodiments and features will be set forth in part in the description which follows. The features and advantages of the disclosed embodiments can be realized and achieved by means of the means, combinations and methods described herein.

Systems and methods are described for processing a film on a surface of a substrate. The system has an aerosol generator that forms droplets from a condensed substance (liquid or solid) of one or more precursors. The carrier gas flows through the condensed material and pushes the droplets toward the substrate placed in the substrate processing region. An inline mechanical pump coupled to the aerosol generator can also be used to push the droplets toward the substrate. A direct current (DC) electric field is applied between two electrically conductive sheets that are configured to pass the droplets between the two electrically conductive sheets. The size of the droplets is reduced as needed by the application of the DC electric field. After passing through the DC electric field, the droplets enter the substrate processing region and chemically react with the substrate to deposit or etch a thin film.

It is desirable to broaden a set of available chemical precursors that can be used in, for example, CVD, atomic layer etch (ALEt) and atomic layer deposition (ALD) chambers. Low vapor pressure solid precursors and high boiling liquid precursors have been difficult to deliver in the vapor phase to CVD, ALET or ALD chambers. This limits the use of precursors in the deposition of thin film materials. Improved delivery of solid and low vapor pressure liquids into the processing chamber can particularly improve the deposition of films containing more than one element. Self-assembled monolayers (SAM) can especially benefit from the use of low vapor pressure precursors. Semiconductor thin film forming applications benefit from a dry deposition process (vapor phase) rather than a liquid deposition process.

Embodiments described herein may relate to solid precursors and/or liquid precursors having a low vapor pressure. Liquids and solids (or combinations thereof) can generally be described as condensing materials. The condensed material consists of atoms/molecules that are always affected by the forces exerted by adjacent atoms/molecules, and may be defined as materials with little or no mean free path, depending on the embodiment. In embodiments, a solid precursor having a low vapor pressure may be dissolved in a single solvent or a mixture of compatible solvents, and such a combination may be referred to as a condensed material. The aerosol is formed from a condensed material and can be formed using an ultrasonic humidifier. The ultrasonic humidifier can have a piezoelectric transducer that can operate at one or more frequencies. The ultrasonic humidifier can generate aerosol droplets that are carried into the reaction chamber (substrate processing region) using a carrier gas such as nitrogen (N ₂ ) or argon (Ar). The carrier gas can be inert and neither form covalent chemical bonds with the condensed material nor form covalent chemical bonds with the substrate. An inline mechanical pump coupled to the aerosol generator can also be used to push the droplets toward the substrate.

Aerosol droplets can pass through a conduit that is heated to prevent condensation or to cause reaction with the substrate after the aerosol droplets enter the substrate processing region. The substrate processing region is within the substrate processing chamber and is a vacuum chamber that evacuates atmospheric gases prior to delivery of the precursor into the substrate processing region. In an embodiment, the substrate processing region is sealed to insulate the outside atmosphere and can operate at a much lower pressure than atmospheric pressure to evacuate atmospheric gases. The condensate precursor does not need to be volatile to form aerosol droplets. The condensate precursor can be dissolved in a solvent or a mixture of solvents from which aerosol droplets are produced. Due to the embodiments described herein, a wider range of precursors can now be used because volatility is no longer necessary. The substrate processing chamber may also be configured with two electrodes that generate an electric field. It has been found that the electric field can reduce the size of the aerosol droplets or maintain the smaller size of the aerosol droplets as desired.

For a better understanding and understanding of the embodiments described herein, reference is now made to FIGS. 1 and 2, which are flow diagrams of film forming processes (101 and 201) in accordance with an embodiment. Reference will be made to FIG. 5A, which includes a cross-sectional schematic view of a substrate processing chamber 1001 in accordance with an embodiment. Any of the substrate processing chambers of Figures 5A, 5B, 5C, or combinations thereof, can be used to perform the processes described herein (e.g., 101 or 102). In process 101, in operation 110, substrate 1013 is delivered into a substrate processing region of substrate processing chamber 1001. The substrate 1013 is supported by a substrate pedestal 1014 that can be resistively heated and/or cooled by passing thermally controlled liquid through the substrate pedestal 1014. A portion of the substrate pedestal and the entire substrate 1013 are shown within the substrate processing region. The substrate processing region is additionally defined by a quartz baffle 1012 and a quartz outer casing 1016, which may be included to reduce the temperature of the chamber body 1006 in a beneficial manner during the film formation process.

In operation 120, the solid precursor is dissolved in a solvent and placed in an aerosol generator 1003-1 having a piezoelectric transducer 1004-1. In operation 130, the carrier gas is heated in the heated carrier gas source 1002 and the carrier gas stream is introduced into the aerosol generator 1003-1. The piezoelectric transducer 1004-1 is vibrated by applying an oscillating voltage to the top and bottom of the transducer, and aerosol droplets are generated from the precursor solution in the aerosol generator 1003-1 (operation 140). Additionally, in operation 140, aerosol droplets flow through the precursor conduit 1015-1 and through the cap 1005 into the substrate processing chamber 1001. The aerosol droplets also flow through the top electrode 1009 before entering the substrate processing region containing the substrate 1013, and then flow through the bottom electrode 1010. A DC electric field is applied between the top electrode 1009 and the bottom electrode 1010 while the aerosol droplets pass between the two electrodes (operation 150). An electric field is applied in the electric field region 1011 and directed from the top electrode 1009 to the bottom electrode 1010. Insulator 1008 is configured to maintain electrical separation between top electrode 1009 and bottom electrode 1010. In an embodiment, the chamber body 1006 and the top cover 1005 can also be electrically insulated from one or both of the top electrode 1009 and the bottom electrode 1010. The DC voltage difference is generated within the DC power source 1007 and is passed into the substrate processing region by means of a vacuum compatible electrical feedthrough. In an embodiment, the smaller size of the aerosol droplets is reduced or maintained by applying a DC electric field perpendicular to the major plane of the substrate 1013. Top electrode 1009 and bottom electrode 1010 have perforations that allow aerosol droplets to pass through, but the two are also planar and each are parallel to the major plane of substrate 1013. The substrate can also be electrically biased during deposition. In operation 160, a film is deposited from the aerosol droplets on the substrate 1013, and in operation 170, the substrate is removed from the substrate processing region.

Aerosol generator 1003 can be positioned proximate to substrate processing chamber 1001 to further maintain a smaller aerosol droplet size. The volume within the aerosol generator 1003 can be approximately proportional to the area of the substrate to be processed. For example, for a 300 mm substrate, a one liter aerosol generator 1003 can be used to create aerosol droplets. A mass flow controller can be used to control the flow of aerosol droplets within the precursor conduit 1015-1 to the substrate processing chamber 1001. The precursor conduit 1015-1 may contain heated activated carbon to maintain the high temperature (above room temperature) of the aerosol droplets, which also helps maintain a smaller aerosol droplet size.

For the film forming process 101, a solid precursor has been used. In an embodiment, a solid or liquid precursor may have been used, and the solid precursor exemplarily exhibits technical effectiveness in accommodating a low vapor pressure precursor. In the next examples, liquid precursors are used, but in embodiments, solid precursors can be substituted for liquid precursors. In operation 210, the substrate is placed in the substrate processing region.

The liquid precursor is placed in an aerosol generator 1003-2 with embedded transducer 1004-2. The carrier gas is heated in the heated carrier gas source 1002 and the carrier gas is introduced into the aerosol generator 1003-2. The transducer 1004-2 is vibrated by applying an oscillating voltage to the top and bottom of the transducer, and aerosol droplets are generated from the precursor solution in the aerosol generator 1003-2 (operation 220). According to an embodiment, the liquid precursor may also be dissolved in a solvent or a combination of compatible solvents, as is the case with the solid precursor of the first example. Next, the aerosol droplets flow through the precursor conduit 1015-2 and through the top cover 1005 into the substrate processing chamber 1001. In operation 230, the aerosol droplets then flow through the top electrode 1009 and through the bottom electrode 1010 before entering the substrate processing region containing the substrate 1013. Before entering the substrate processing region, a DC electric field is applied between the top electrode 1009 and the bottom electrode 1010 while aerosol droplets pass between the two electrodes. An electric field is applied in the electric field region 1011 and directed from the top electrode 1009 to the bottom electrode 1010. Insulator 1008 is configured to maintain electrical separation between top electrode 1009 and bottom electrode 1010. The DC voltage difference is generated within the DC power source 1007 and is passed into the substrate processing region by means of a vacuum compatible electrical feedthrough. In an embodiment, the smaller size of the aerosol droplets is reduced or maintained by applying a DC electric field perpendicular to the major plane of the substrate 1013. Top electrode 1009 and bottom electrode 1010 have one or more perforations that allow aerosol droplets to pass through, but the two are also planar and each are parallel to the major plane of substrate 1013. In an embodiment, the pedestal can be electrically biased relative to the chamber body 1006, the top electrode 1009, and/or the bottom electrode 1010.

A thin film is deposited on the substrate 1013 from smaller aerosol droplets. The substrate processing region can be evacuated to remove unreacted aerosol droplets and reaction byproducts. A second precursor having different chemical properties then flows into the substrate processing region (operation 240) for completing the formation of an "atomic" layer deposited film (ALD) in operation 250. If the target thickness has not been reached, the process can be repeated (operation 260). Once the target thickness is reached, in operation 270, the substrate is removed from the substrate processing region. In general, the precursors can be delivered to the substrate processing zone in a sequential, alternating manner, as in the examples, or according to embodiments, they can enter the reactor simultaneously. In an embodiment, the precursors may be combined with each other prior to entering the substrate processing region.

The benefits of the processes and equipment described herein may involve a reduction in processing time. It has been found that film formation using low vapor precursors often takes hours and even tens of hours to achieve a beneficial film thickness. In accordance with embodiments, the techniques and hardware described herein can be used to reduce film etch/filming time by more than 100 to over 1000 times. In an embodiment, the etch/deposition time can be between 5 seconds and 5 minutes, or between 15 seconds and 2 minutes. The vapor etch or vapor deposition techniques described herein are "dry" processes in which the reaction is dominated by chemical reactions on the surface of the gas. Some prior art processes involve immersing a patterned substrate in a liquid solution containing a low vapor pressure precursor to achieve a desired etch or deposition rate. Herein, the precursor is delivered to the substrate in the gas phase, and the process can thus be described as a dry process. The dry process described herein avoids damage to the patterned substrate of small line widths due to surface tension of the liquid treatment. The benefits of dry processes and equipment include achieving high etch/deposition rates while avoiding pattern damage.

In all of the embodiments described herein, the precursor is in the condensed matter phase, which may include dissolution in a solvent. In embodiments, the vapor pressure of the condensate precursor may be zero, as low as unmeasurable, below 10 Torr, below 20 Torr, or below 30 Torr before dissolution (or if not used at all). According to an embodiment, after dissolution, the vapor pressure of the solution containing the condensate precursor and a suitable solvent may be 10 Torr, less than 30 Torr or less than 50 Torr. An exemplary condensate precursor will be presented after introduction of a motivating deposition application.

An exemplary deposition application that can benefit from the techniques and hardware described herein is to form a self-assembled monolayer, which can involve the use of a low vapor pressure liquid precursor. The benefit of the deposition process described herein is the fine and complex patterning of the extremely conformal deposition rate on the substrate. Deeper gaps, trenches, or vias tend to exhibit higher deposition rates near their openings than deeper portions of the trench, especially if the droplet size is larger than the feature size or line width. when. According to an embodiment, the method described herein can be used to deposit a conformal having a uniform or relatively uniform thickness between 0.5 nm and 20 nm, between 1 nm and 10 nm, or between 2 nm and 5 nm. Conformal film. The method can alternatively be used to etch at a uniform etch rate, regardless of how complex the patterning on the patterned substrate is. In an embodiment, the width and depth of the vias or trenches (features) may be between 3 nm and 20 nm or between 5 nm and 10 nm. All of the parameters described herein are applicable to both etching and deposition, but illustrative examples describe deposition processes. In embodiments, the width of the vias or trenches (in a narrower dimension) may be less than 30 nm, less than 20 nm, or less than 10 nm. Depth is measured herein from the top to the bottom of the trench. "Top", "Upper" and "Upward" will be used herein to describe a portion/direction that is perpendicularly away from the plane of the substrate and that is further away from the principal plane of the substrate in the vertical direction. "Vertical" will be used to describe objects that are aligned toward the "top" in the "up" direction. Other similar terms may also be used, the meaning of which will now be clear.

An exemplary low vapor pressure precursor includes a precursor that can be used to form a self-assembled monolayer (SAM). The techniques described herein can be used in many places other than those presented below, although illustrative examples can be helpful in understanding the embodiments disclosed herein. The precursor for depositing the self-assembled monolayer may have a tail moiety (TM) chemically distinguished from the head moiety (HM), which has been found to form a self-assembled monolayer. Said to be beneficial. The precursor may be phosphoric acid, and the phosphoric acid includes HM having the chemical formula PO(OH)2. According to an embodiment, the low vapor pressure condensate precursor may comprise octyl phosphate (CH ₃ (CH ₂ ) ₆ CH ₂ -P(O)(OH) ₂ ), perfluorinated octyl phosphate (CF ₃ (CF ₂ )) ₅ CH ₂ -CH ₂ -P(O)(OH) ₂ ), octadecylphosphonic acid (CH ₃ (CH ₂ ) ₁₆ CH ₂ -P(O)(OH) ₂ ), decylphosphonic acid, three One or more of tolylphosphonic acid, cyclohexylphosphonic acid, hexylphosphonic acid or butylphosphonic acid.

The tail portion (TM) can prevent or hinder film formation on the patterned layer during subsequent exposure to the second deposition precursor. According to an embodiment, the tail portion of the phosphoric acid precursor may comprise a perfluorinated alkyl group having more than 5 carbon atoms, more than 6 carbon atoms, or more than 7 carbon atoms covalently bonded to each other in the chain. For smaller carbon chains, the presence of larger fluorine atoms as a replacement for much smaller hydrogen atoms appears to hinder the nucleation of the patterned layer. In embodiments, the tail portion of the phosphoric acid precursor can include an alkyl group having more than 12 carbon atoms, more than 14 carbon atoms, or more than 16 carbon atoms covalently bonded in the chain. According to an embodiment, TM may comprise linear or aromatic hydrocarbons, such as _{-CH 2, C 6 H 5,} C 6 H 4, C 2 H 5 or -CH ₂ CH ₂ CH _3.

A precursor for depositing a self-assembled monolayer (SAM) can provide a covalent bond to the head portion of the substrate, and a tail portion extending from the covalent bond away from the substrate. The tail portion includes a relatively long sequence of covalent bonds called chains. In an embodiment, the SAM can be stabilized (resist decomposition) up to 300 ° C or 350 ° C substrate temperature. The HM of the chemical precursor molecule may comprise a sulfur-containing group, such as a thiol group. According to an embodiment, the precursor may be methyl mercaptan (CH ₃ SH), ethanethiol (C ₂ H ₅ SH) or butyl mercaptan (C ₄ H ₉ SH), N-alkyl mercaptan {CH ₃ (CH) ₂ ) _n-1 SH, where n is ₈ , 12, ₁₆ , 18, 20, 22 or 29}. In embodiments, the precursor may be one or more of CF ₃ and CF ₂ terminated thiols, such as CF ₃ (CF ₂ ) n(CH ₂ ) ₁₁ )SH and CF ₃ (CF ₂ ). ₉ (CH ₂ ) _n SH (where n is 2, 11 or 17), and n is 9-15 (CF ₃ (CH ₂ ) _n SH). According to an embodiment, the head group may comprise a nitrogen-containing group. In an embodiment, the precursor may be 3-aminopropyltriethoxysilane (APTES), (3-aminopropyl)trimethoxysilane (APTMS), 1,3 diamino One or more of propane, ethylenediamine, ethylenediaminetetraacetic acid, diethylamine and methylamine.

The rate at which the film is deposited onto the patterned layer on the SAM can be much lower than the rate at which the film is deposited onto portions that are not covered by the self-assembled monolayer. The rate at which the film is deposited on the SAM can be reduced by the presence of SAM, and this deposition rate can be much lower than in the absence of SAM. In embodiments, the rate of deposition on the portion without SAM may be greater than 100 times, greater than 150 times, or greater than 200 times the rate of growth on the SAM portion. The presence or absence of the SAM layer can be determined by the difference in affinity between the low vapor pressure precursor and the different exposed portions on the patterned substrate. For example, the deposition rate of the SAM can be easily performed on the exposed metal portion, but not on the exposed dielectric portion of the patterned substrate. The metal portion may be electrically conductive and may comprise or consist of such elements (if no other elements are present) that form a conductive material in a condensed matter state. In embodiments, the deposition rate of the SAM layer on the exposed metal portion can be 10, 15, 20, or 25 times greater than the deposition rate on the exposed dielectric portion.

In embodiments, the precursor may be deposited on two or more chemically distinct portions of the patterned layer, but a covalent bond may be formed on only one of the two portions. In another part, the precursor can be bonded by physisorption, which means that no covalent bond is formed between the precursor and the second exposed surface portion. In this scenario, the physically adsorbed precursor can be easily removed while allowing the chemisorb (covalently bonded) precursor to remain. This is an alternative method for producing a selectively deposited SAM layer.

A self-assembled monolayer (SAM) grown as described herein can be selectively deposited on portions of the patterned substrate, but not deposited on other portions. Subsequent deposition can then be carried out on areas without SAM coating. The method described herein saves cost and improves overlay accuracy compared to conventional methods involving lithographic patterning. Subsequent deposition may also be referred to as selective deposition after selective deposition of the SAM, but the subsequent deposition is a reverse image of the selectively deposited SAM layer. Subsequent deposited films may have greater utility (as compared to SAM) in the operation of the completed integrated circuit or in additional processing. 3A, 3B, and 3C are side views of patterned substrates at certain points during or after selective deposition of self-assembled monolayer 310 and selectively deposited dielectric 315-1. In FIG. 3A, a self-assembled monolayer 310 is deposited on exposed copper 305 located in a gap within patterned substrate 301, but not deposited on other exposed portions. The exposed copper 305 may be bare, i.e., there may be no liner layer or barrier between the top of the copper 305 and the self-assembled monolayer 310.

Figure 3B shows a selectively deposited dielectric 315-1 formed at a location free of self-assembled monolayers, in the example, anywhere other than copper. Each self-assembled monolayer 310 can be removed to leave a selectively deposited dielectric 315-1, with the exception of the embedded copper 305 in the gap of the patterned substrate 301, as shown in Figure 3C. 3D is a side view of a patterned substrate after selective deposition of a self-assembled monolayer, not disclosed herein. Prior art methods of forming self-assembled monolayers have been tested using the process flow of Figures 3A-3C and tend to produce selectively deposited dielectric 315-2, a selectively deposited dielectric 315- 2 overlies the portions of the embedded copper 305 and increases the resistivity within the completed component or causes the completed component to fail.

4 illustrates a diagram of a contact angle without and with a material having an adsorbed self-assembled monolayer, in accordance with an embodiment. The contact angle was measured on each surface by wetting the surface with deionized water and observing the angle formed by the action of water on the various materials. Cerium oxide, low dielectric constant dielectric, copper and titanium nitride were characterized to measure the contact angle, and four materials were shown from left to right. Each dashed rectangle in Figure 4 represents one of four materials and contains two measurements: one measurement from the bare surface and one measurement after exposure to octadecylphosphonic acid (referred to as ODPA) . Only copper showed a statistically significant difference between the exposed surface and the surface exposed to octadecylphosphonic acid. The lack of a difference between the exposed surface and the exposed surface demonstrates that octadecylphosphonic acid is not chemisorbed onto each of yttrium oxide, low dielectric constant dielectric, and titanium nitride. In an embodiment, a self-assembled monolayer can be formed on portions of the patterned substrate (eg, copper) without forming on another portion. According to an embodiment, subsequent deposition may be performed only on the area without the SAM coating.

Illustrative solvents that can be used to dissolve low vapor pressure condensate precursors can include isopropanol (IPA), 1-butanol, toluene, xylene, benzene, hexane, cyclohexane, tetrahydrofuran, two, depending on the embodiment. One or more of sulfonium, dimethylformamide, acetonitrile, dichloromethane, ethyl acetate, and chloroform. In embodiments, the solvent may comprise an aromatic hydrocarbon, may comprise or consist of carbon and hydrogen, or may comprise or consist of carbon, hydrogen and oxygen.

5A shows a cross-sectional schematic view of a substrate processing chamber that can be used to perform the methods described above, in accordance with an embodiment. The substrate temperature can rise above room temperature during deposition, depending on the type of film being grown. The dry process described herein enables the process to be performed at higher temperatures than prior art liquid processes. The smaller aerosol droplets can exit the aperture of the quartz baffle 1012, then approach and contact the substrate 1013 while the substrate is maintained between 100 ° C and 800 ° C, between 200 ° C and 700 ° C at 300 ° C. Temperature between 600 ° C or between 400 ° C and 500 ° C. These substrate temperatures can be present in all of the deposition operations described herein. The chamber body 1006 and/or the top cover 1005 can be a stainless steel (eg, SST 304 or preferably SST 316) material that can withstand relatively high temperatures (possibly up to 400 ° C) while maintaining the quartz baffle 1012 / quartz Vacuum integrity between the substrate processing region within the outer casing 1016 and the atmosphere outside of the chamber body 1006 and the top cover 1005. The chamber body 1006, the top cover 1005, and any other components may be sealed with an O-ring that is compatible with a particular process environment to ensure gas between the substrate processing region and the atmosphere outside the substrate processing chamber 1001. isolation.

The chamber body 1006 and/or the top cover 1005 can be cooled by flowing a coolant through a coolant passage that is machined or formed, for example, from stainless steel. A coolant passage may be placed adjacent the O-ring connector to prevent the O-ring from being exposed to high temperatures. To safely or reduce the base pressure within the quartz baffle 1012 and the quartz outer casing 1016 (substrate processing area), the temperature of the top cover 1005 and/or the chamber body 1006 can be maintained below 70 °C during film formation. The presence of the quartz baffle 1012 and the quartz outer casing 1016 may further contribute to a reduction in the operating temperature of the top cover 1005 and/or the chamber body 1006. Quartz baffle 1012 (eg, a quartz portion with voids), top electrode 1009, and/or bottom electrode 1010 can remain below 100 °C during film formation. The substrate pedestal 1014 can be heated to the previously given desired temperature of the substrate 1013 and maintain the temperature of the substrate 1013 at a level that facilitates the process. The substrate pedestal 1014 is vertically adjustable to provide flexibility in positioning the substrate 1013 relative to the bottom of the quartz baffle 1012. The thermocouple can be attached to the top cover 1005 and/or the chamber body 1006 or embedded within the top cover 1005 and/or the chamber body 1006 to provide feedback control of temperature and/or coolant flow. The thermocouple can also be used to stop the precursor flow when the safe temperature upper limit set point is exceeded, and also to stop heating the substrate base 1014.

In embodiments, the pressure in the substrate processing region during the deposition process described herein may be between 10 Torr and 750 Torr, between 20 Torr and 700 Torr, or between 100 Torr and 600 Torr. According to an embodiment, the reaction is thermally performed, only excited by the temperature of the substrate itself. In embodiments that rely on substrate temperature to effect a deposition reaction, the term "plasma-free" can be used herein to describe a substrate processing region during applications that do not use or substantially use plasma power. The lack of plasma in the substrate processing region will be quantified in several complementary ways that can be used separately or in combination. The plasma power can also be kept below a small threshold amount to enable proper reaction. In embodiments, the plasma power applied to the substrate processing region may be less than 100 watts, less than 50 watts, less than 30 watts, less than 10 watts, and may be 0 watts.

The lack of any local plasma (or reduced magnitude) is satisfactory in making the deposition process more conformal and less likely to deform the features. The term "plasma-free" will be used herein to describe a substrate processing region during which plasma power is not applied or substantially not applied to the substrate processing region. In another aspect, according to an embodiment, the electron temperature in the substrate processing region can be less than 0.5 eV, less than 0.45 eV, less than 0.4 eV, or less than 0.35 eV. In an embodiment, the low vapor pressure precursor is not excited in any of the far end plasmas prior to entering the substrate processing region. For example, it may be present in the distal plasma region or in the separate chamber region and used to direct aerosol droplets toward the substrate processing region and any distal region may be plasma free as defined herein.

A gap (shown as electric field region 1011 in FIG. 5A) exists between top electrode 1009 and bottom electrode 1010. The gap forming the electric field region 1011 is measured between the top surface of the bottom electrode 1010 and the bottom surface of the top electrode 1009. According to an embodiment, the height of the electric field region 1011 may be between 0.5 mm and 10 mm or between 1 mm and 3 mm. In an embodiment, the voltage applied between the top electrode 1009 and the bottom electrode 1010 to maintain or achieve a smaller aerosol droplet size may be a DC voltage that places the top electrode 1009 at a positive potential relative to the bottom electrode 1010, or The bottom electrode 1010 is placed at a negative potential DC voltage with respect to the top electrode 1009. According to an embodiment, the magnitude of the DC voltage difference can be between 100 volts and 2 kilovolts, between 200 volts and 1000 volts, or between 500 volts and 800 volts. In an embodiment, the DC electric field between the top electrode 1009 and the bottom electrode 1010 may have between 500 V/cm and 20000 V/cm, between 1000 V/cm and 10000 V/cm, or at 2000 V/cm. Amplitude between 7000 V/cm. According to embodiments, it has been found that by applying a DC electric field, smaller diameter droplets are reduced, or their size is maintained, even if the aerosol droplets are uncharged and non-polar.

Additional benefits of the hardware and processes described herein will now be described. Prior art aerosol droplets already have a diameter between about 0.5 [mu]m and a few [mu]m. Several problems arise due to the presence of larger diameter droplets that deliver precursors to the substrate. According to an embodiment, the aerosol droplets formed here may have a diameter between 3 nm and 75 nm, between 5 nm and 50 nm or between 10 nm and 25 nm. The smaller aerosol droplet size contributes to the penetration of the precursor source into the smaller features on the patterned substrate. Smaller sizes can result in enhanced material gap filling and fewer trapped voids in the gap. Smaller sizes also enable more conformal deposition due to the ability to penetrate narrow gaps. The smaller size of the aerosol droplets also increases the surface to volume ratio, which allows for the faster release of elements present in low vapor pressure precursors (and solvents if solvents are used). Some elements are undesirable in deposited films. The smaller droplet sizes described herein are such that undesirable elements (e.g., carbon or hydrogen) form volatile materials that are readily detached from the surface during the deposition reaction. Additional benefits include reduced surface roughness and reduction in the number and size of grain boundaries achieved using the techniques described herein.

Smaller aerosol droplets can be produced in the aerosol generator 1003 using ultrasonic agitation. As noted above, the size of the aerosol droplets can be reduced (or their growth prevented) by applying a DC electric field in the electric field region 1011 before the aerosol droplets enter the substrate processing region. A particle screening program 1019 can be installed downstream of the aerosol generator 1003 to further reduce the size of aerosol droplets that are allowed to pass through the precursor conduit 1015, through the electric field region 1011, and into the substrate processing region. According to an embodiment, the particle screening program 1019 may allow aerosol droplets having a diameter of less than 0.3 [mu]m, less than 0.25 [mu]m, or less than 0.2 [mu]m to pass through while inhibiting or preventing droplet flow having diameters greater than these size thresholds. The screening program can be placed anywhere along the precursor conduit 1015, including at a location directly above the top electrode 1009. In an embodiment, the screening program can be located in the top electrode 1009, can be in the electric field region 1011, can be in the bottom electrode 1010, or even downstream of the bottom electrode 1010. The size of the aerosol droplets can be measured using an in situ particle size analyzer such as a condensed particle counter or detector.

During all of the deposition operations described herein, the vacuum pump 1017 can be used to evacuate the substrate processing region within the substrate processing chamber 1001 prior to introducing the aerosol droplets into the substrate processing region. Some chemicals may need to be further processed after passing through vacuum pump 1017 before being released into the atmosphere. A scrubber 1018 can be placed downstream of the vacuum pump 1017 to modify or remove the chemical composition of the process effluent prior to releasing the process effluent. A closed loop emissions feedback system can be used to maintain the desired pressure within the substrate processing area. If the pressure in the substrate processing region is measured as a pressure higher than the set value (or an overpressure condition), an automatic valve (not shown) can release the pressure within the substrate processing chamber 1001, causing the substrate processing region to the vacuum pump 1017 and The scrubber 1018 is open.

The devices and techniques described herein can be used to etch or form a variety of layers, including metals, semiconductors, and insulators. According to embodiments, the layers may be conformal and may be a self-assembled monolayer (SAM) formed by organic or inorganic molecules or atomic layer deposition (ALD). Merely exemplified, thin films that can be etched or deposited using these techniques include indium gallium arsenide, indium gallium phosphide, gallium arsenide, and titanium oxide. In an embodiment, the film can be a metal oxide, a III-V semiconductor, or a II-VI semiconductor.

Figure 5A shows two aerosol generators (1003-1 and 1003-2) for delivering a low vapor pressure precursor into a substrate processing region. There may be more than two aerosol generators, and they may be enhanced by a non-aerosol generating source, which is not shown in the drawings for added readability. The transducers in one or more of the aerosol generators can alternatively be left off to provide the non-aerosol generating source with the illustrated hardware. During film growth, one or more of the aerosol generating sources can be used to deliver dopants to the film, as can be used to grow semiconductors doped with electron acceptors or donors. In this manner, an n-type or p-type semiconductor (eg, germanium) can be formed using the techniques and hardware described herein.

FIG. 5B illustrates a cross-sectional schematic view of another substrate processing chamber 1101, which may also be used to perform the foregoing methods, in accordance with an embodiment. Features and elements of each embodiment may be added to some or all of the features and elements of another embodiment to provide additional embodiments. The substrate 1113 is placed in the substrate processing region of the substrate processing chamber 1101 for deposition. The substrate 1113 is supported on the bottom electrode 1114. The carrier gas flows from the carrier gas source 1102 through the carrier gas supply valve 1104 into the aerosol generator 1110. The RF power source 1106 is configured to supply an alternating current signal (eg, ultrasound) to a piezoelectric transducer 1108 that is placed in physical contact with the aerosol generator 1110. The piezoelectric transducer 1108 evaporates a condensate precursor source (eg, solid or liquid), and the carrier gas from the carrier gas source 1102 flows through the aerosol generator 1110 and passes the vaporized precursor through the chamber inlet valve. 1111 is carried into the substrate processing region of the substrate processing chamber 1101. The carrier gas may be heated prior to passing through the carrier gas supply valve 1104 and entering the aerosol generator 1110 as previously described.

The bottom electrode 1114 is parallel to the top electrode 1112 and evaporated precursor or aerosol droplets are delivered between the electrodes into the substrate processing region. Figure 5A shows aerosol droplets delivered through one of these electrodes, and Figure 5B shows a configuration that does not require flow through the electrodes. A DC power source (not shown at this time) is configured to apply a DC voltage between the top electrode 1112 and the bottom electrode 1114 to achieve or maintain a smaller droplet size in the evaporated precursor in the substrate processing region. An electric field is directed from the top electrode 1112 to the bottom electrode 1114. An electrical insulator is disposed between the top electrode 1112 and the bottom electrode 1114 to ensure an independently controllable voltage level. In an embodiment, the DC voltage difference is generated within the DC power source and may be applied to the top electrode 1112 and the bottom electrode 1114 using a vacuum feedthrough, or applied directly to the electrodes without first passing through the vacuum. In an embodiment, the smaller size of the aerosol droplets is reduced or maintained by applying a DC electric field perpendicular to the substrate 1113. In an embodiment, top electrode 1112 and bottom electrode 1114 are planar and are each parallel to a major plane of substrate 1113. The substrate can be electrically biased during deposition. A thin film is deposited on the substrate 1113 from the aerosol droplets. Unreacted precursors or other process effluents can be pumped using a vacuum pump 1118, and the scrubber 1120 can be used to chemically modify the process effluent to improve environmental compatibility.

A heater coil 1116 can be disposed on the top electrode 1112 and/or the bottom electrode 1114. Heating the top electrode 1112 and/or the bottom electrode 1114 prevents the vaporized precursor from condensing and further reducing the droplet size. The substrate temperature can rise above room temperature during deposition, depending on the type of film being grown. The dry process described herein enables the process to be performed at higher temperatures than prior art liquid processes. According to an embodiment, while the evaporated precursor is in contact with the substrate 1113, the substrate is maintained between 100 ° C and 800 ° C, between 200 ° C and 700 ° C, between 300 ° C and 600 ° C or between 400 ° C and 500 ° C. The temperature between. Process pressure is also given before, and for the sake of brevity, it will not be repeated here. According to an embodiment, the reaction can be carried out thermally, only by the temperature of the substrate itself. The substrate processing region can be described as being free of plasma and its definition has previously been presented. According to an embodiment, the gap between the top electrode 1112 and the bottom electrode 1114 may be between 1.0 mm and 10 mm or between 1.5 mm and 3 mm. Voltage, electric field strength, droplet size, and process benefits have previously been presented.

FIG. 5C illustrates a cross-sectional schematic view of another substrate processing chamber 1201 that may also be used to perform the methods described above, in accordance with an embodiment. Features and elements of each embodiment may be added to some or all of the features and elements of another embodiment to provide additional embodiments. The substrate 1215 is placed in the substrate processing region of the substrate processing chamber 1201 prior to deposition. The substrate 1215 is supported on the substrate base 1216. Substrate pedestal 1216 can be a vacuum compatible material, in an embodiment an electrical insulator. Substrate pedestal 1216 can be further configured to be vacuum compatible at the substrate temperatures described herein. In an embodiment, the substrate pedestal 1216 can be a carbon block and can comprise or consist of carbon. The carrier gas flows from the carrier gas source 1202 into the aerosol generator 1210 and is permeable to the liquid precursor 1206. An RF power source (not shown) is configured to supply an alternating current signal (eg, ultrasound) to a piezoelectric transducer 1204 disposed within the aerosol generator 1210. Piezoelectric transducer 1204 can vibrate to beneficially facilitate the transport of aerosol droplets of liquid precursor 1206 toward the substrate processing region of substrate processing chamber 1201.

In this particular embodiment, the electrodes are vertically aligned. The first electrode 1214 is also parallel to the second electrode 1218, and the vaporized precursor or aerosol droplets are delivered through the first electrode 1214 to the substrate processing region between the two electrodes. Figure 5A shows aerosol droplets delivered through one of these electrodes, and Figure 5C shows a configuration with this common property. A DC power source (not shown at this time) is configured to apply a DC voltage between the first electrode 1214 and the second electrode 1218 to achieve or maintain a smaller droplet size in the evaporated precursor in the substrate processing region. An electric field is directed from the first electrode 1214 to the second electrode 1218. All direct connections between the first electrode 1214 and the second electrode 1218 are electrically insulated. In an embodiment, the inlet sheet 1212 can also be electrically isolated from the first electrode 1214 by inserting an inlet insulator 1213 between the first electrode 1214 and the inlet sheet 1212. Similarly, the exit sheet 1220 can be electrically isolated from the second electrode 1218 by inserting an exit insulator 1219 between the second electrode 1218 and the exit sheet 1220. In an embodiment, the DC voltage difference is generated within the DC power source and may be applied to the first electrode 1214 and the second electrode 1218 using a vacuum feedthrough, or directly to the electrodes without first passing through the vacuum. In contrast to each of the embodiments depicted in Figures 5A and 5B, in an embodiment, the smaller size of the aerosol droplets is reduced or maintained by applying a DC electric field parallel to the substrate 1215. In an embodiment, first electrode 1214 and second electrode 1218 are planar and are each perpendicular to a major plane of substrate 1215. A film is deposited from the aerosol droplets on the substrate 1215. According to an embodiment, unreacted precursor or other process effluent may be pumped through second electrode 1218, outlet insulator 1219, and outlet plate 1220. Process effluent can be pumped by vacuum pump 1222. Substrate temperature, process pressure, electric field strength, droplet size, and process benefits have previously been presented.

Figure 6 shows a schematic control diagram of a deposition technique comprising a method according to an embodiment. Wet spray pyrolysis, dry spray pyrolysis, aerosol assisted CVD (methods herein) and powder spray pyrolysis are each presented in Figure 6 and compared. Both wet spray pyrolysis and dry spray pyrolysis, aerosol assisted CVD (AACVD), and powder spray pyrolysis can each have the ability to form larger droplets 1511. In the case of dry spray pyrolysis, AACVD, and powder spray pyrolysis, larger droplets 1511 can be separated from carrier fluid 1512. Various aspects of the devices and methods described herein are used to reduce the size of the droplets and maintain a smaller size to evaporate the precursor 1531. The desired uniformity of the film 1541 is achieved by reducing the size of the precursor amalgamation to and including the individual molecular components. A uniform film 1541 is formed on the substrate 1551 while still forming agglomeration in each of wet spray pyrolysis, dry spray pyrolysis, and powder spray pyrolysis.

The examples discussed so far use a low vapor pressure precursor to deposit a thin film on a substrate by alternating or continuous exposure. The techniques described herein can also be used to perform etching by exposure to an etch precursor (etchant) having a low vapor pressure in alternating or continuous exposure. In embodiments, the low vapor pressure etchant can be a halogen containing precursor, a fluorine containing precursor, a chlorine containing precursor, or a bromine containing precursor. According to an embodiment, the low vapor pressure etchant may be a metal and halogen containing precursor, wherein the halogen may be fluorine, chlorine or bromine. Similarly, in embodiments, the low vapor pressure etchant can be a halide (eg, an alkyl halide). The low vapor pressure etchant can have a long alkyl chain, as described elsewhere herein, which is associated with a low vapor pressure remedy by the techniques presented herein.

In embodiments, the processes described herein may involve removing a single layer each time it is alternately exposed to the first precursor and the second precursor. According to embodiments, the processes described herein may involve performing a single layer of material deposition each time alternately exposed to the first precursor and the second precursor. Both the first precursor and the second precursor can be low vapor pressure precursors prepared using aerosol generating techniques. Alternatively, one of the precursors may be a low vapor pressure precursor that may be prepared using aerosol generating techniques, while the other may have a relatively high vapor pressure and be delivered to the substrate processing region by simpler conventional means.

In all of the embodiments described herein, the low vapor pressure condensate precursor (eg, solid precursor or liquid precursor) can be between 5 mgm (mg/min) and 500 mgm, at 10 mgm and 300 mgm. A flow rate between 25 mgm and 200 mgm. Two or more low vapor pressure condensate precursors may be used, in which case each precursor may have a flow rate between the ranges given above. Other types of precursors can also be used, as can be the case with atomic layer deposition. In any of the embodiments described herein, other precursors may be supplied at a flow rate between 5 sccm and 2000 sccm, between 10 sccm and 1000 sccm, or between 25 sccm and 700 sccm. In an embodiment, the growth rate of the film using the aerosol droplet formation method and the hardware described herein can exceed 300 Å/min compared to the slow deposition rate of prior art aerosol-assisted chemical vapor deposition. More than 500 Å / min, or can exceed 1000 Å / min.

During the atomic layer deposition process, each of the embodiments may have an evacuation operation between successive exposures in sequence. In general, during the alternate exposure of the deposition sequence, all of the deposition operations and etching operations described herein can be simply replaced by a stoppage during the precursor flow into the substrate processing region. Alternatively, a gas can be used to actively purge the substrate processing region that does not substantially exhibit chemical reactivity to the exposed material on the patterned substrate. After the precursor is stopped or actively purged, the next precursor can flow into the substrate processing region to continue etching/deposition of the patterned substrate/etching/deposition on the patterned substrate.

The metal may comprise or consist of a "metal element" which forms a solid conductive material consisting only of the metal element. In an embodiment, a conductive material consisting solely of such a metal element (or a metal in a relatively pure form) may have a conductivity of less than 10-5 Ω-m at 20 °C. According to an embodiment, such a conductive material may form an ohmic contact when combined with another electrically conductive material. The metal regions as described herein may be composed of metal elements or may also be metal nitrides because nitrogen has low electronegativity, which typically enables metal nitrides to maintain electrical conductivity. In an embodiment, the metal nitride may contain a metal element and nitrogen, and may be composed of a metal element and nitrogen. In the exemplary case of tungsten and tungsten nitride, the metal may comprise or consist of tungsten, and the metal nitride may comprise or consist of tungsten and nitrogen.

The advantages and benefits of the processes described herein are the rate of conformal deposition or etching of the material on the substrate. As used herein, terms such as conformal etching, conformal deposition, and conformal film refer to a film or removal speed that conforms to the contour of the patterned surface, regardless of the shape of the surface. The removal rate or the top and bottom surfaces of the deposited layer can be substantially parallel. One of ordinary skill in the art will recognize that the deposition process is most likely not 100% conformal, and thus, the term "substantially" allows for acceptable tolerances. Similarly, a conformal layer refers to a layer having a substantially uniform thickness. The conformal layer can have an outer surface that is identical in shape to the inner surface.

Embodiments of the substrate processing chamber can be incorporated into larger manufacturing systems for producing integrated circuit wafers. Figure 7 illustrates one such substrate processing system (host) 2101 having a deposition chamber, an etch chamber, a bake chamber, and a solidification chamber in an embodiment. In the figure, a pair of front opening unified pods (loading gate chambers 2102) are supplied with substrates of various sizes that are received by the robotic arm 2104 and placed into the substrate processing chambers 2108a-f. One of the ones is placed in the low pressure holding area 2106. The second robotic arm 2110 can be used to transport substrate wafers from the retention area 2106 to the substrate processing chambers 2108a-f and transmit them back. Each of the substrate processing chambers 2108a-f can be assembled to perform a number of substrate processing operations other than loop layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor phase. In addition to deposition (PVD), etching, atomic layer etching, pre-cleaning, degassing, orientation, and other substrate processes, the dry etching process described herein is also included.

As used herein, a "patterned substrate" can be a support substrate with or without layers formed thereon. The patterned substrate can be a plurality of doping concentrations and distributed insulators or semiconductors, and can be, for example, semiconductor substrates of the type used in integrated circuit fabrication. The exposed "metal" of the patterned substrate is primarily a metallic element, but may include minor concentrations of other elemental components such as nitrogen, hydrogen, helium, and carbon. The exposed "metal" may consist of or consist essentially of a metallic element. The exposed "metal nitride" of the patterned substrate is primarily nitrogen and metal elements, but may include minor concentrations of other elemental components such as nitrogen, hydrogen, helium, and carbon. The exposed "metal nitride" may consist of or consist essentially of nitrogen and metal elements. Other examples of layers that can be treated according to the methods described herein include titanium oxide, aluminum oxide, zirconium oxide, titanium-doped cerium oxide, and cerium oxide.

The exposed "矽" or "polysilicon" of the patterned substrate is primarily Si, but may include minor concentrations of other elemental components such as nitrogen, hydrogen, and carbon. The exposed "矽" or "polysilicon" may consist of or consist essentially of 矽. The exposed "tantalum nitride" of the patterned substrate is primarily germanium and nitrogen, but may include minor concentrations of other elemental components such as nitrogen, hydrogen, and carbon. "Exposure tantalum nitride" may consist of or consist essentially of helium and nitrogen. Exposed "silicon oxide" patterned substrate is primarily SiO _2, but may include small amounts of other elements concentration of components (e.g., nitrogen, hydrogen and carbon). In some embodiments, the yttria region etched using the methods disclosed herein consists essentially of ruthenium and oxygen.

The carrier gas described herein can be an inert gas. The phrase "inert gas" refers to any gas that does not form a chemical bond when etched or incorporated into a layer. Exemplary inert gases include noble gases, but other gases may also be included as long as a (usually) trace amount is trapped in the layer without forming a chemical bond.

The gap is an etch geometry with any level aspect ratio. The gap may be circular, elliptical, polygonal, rectangular, or various other shapes as viewed from above the surface. The "groove" is a long gap. The groove may have the shape of a gutter surrounding the island of material, the aspect ratio being the length or perimeter of the gutter divided by the width of the gutter. The "via" is a short gap with a level-to-width ratio. As seen from above, it is almost monolithic. The vias may be round, slightly elliptical, polygonal or slightly rectangular. The vias may or may not be filled with metal to form a vertical electrical connection.

Various modifications, alternative constructions, and equivalents may be employed, without departing from the spirit of the disclosed embodiments. In addition, many well known processes and components have not been described in order to avoid unnecessarily obscuring the disclosed embodiments. Therefore, the above description should not be taken as limiting the scope of the claims.

When a range of values is provided, it is understood that each intervening value between the upper and lower limits of the range (unless the context clearly indicates otherwise, one tenth of the lower limit unit) is also explicitly disclosed. Each smaller range between any stated or intervening value in the stated range and any other stated or intervening value in the stated range is covered. The upper and lower limits of these smaller ranges may be independently included in or excluded from the range, and include any limit, no limit, or both. Each range is also encompassed within the disclosed embodiments, depending on any precisely excluded limit values in the stated range. Where the stated range includes one or both of these limits, it also includes the exclusion of any one or both of those included.

As used herein and in the appended claims, the claims Thus, for example, reference to "a process" includes a plurality of such processes, and reference to "dielectric material" includes reference to one or more dielectric materials and equivalents known to those skilled in the art, and the like.

In addition, the terms "including" and "comprising" are used in the specification and the claims, The presence or addition of an integer, component, step, action, or group.

101‧‧‧Process
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230‧‧‧ operations
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250‧‧‧ operations
260‧‧‧ operation
270‧‧‧ operation
301‧‧‧ patterned substrate
305‧‧‧ copper
310‧‧‧Self-alone single layer
315-1‧‧‧Dielectric
315-2‧‧‧ dielectric
1001‧‧‧Substrate processing chamber
1002‧‧‧ carrier gas source
1003-1‧‧‧ aerosol generator
1003-2‧‧‧ aerosol generator
1004-1‧‧‧Piezoelectric transducer
1004-2‧‧‧Embedded transducer
1005‧‧‧ top cover
1015-1‧‧‧Precursor catheter
1015-2‧‧‧Precursor catheter
1006‧‧‧ chamber body
1007‧‧‧DC power supply
1008‧‧‧Insulator
1009‧‧‧Top electrode
1010‧‧‧ bottom electrode
1011‧‧‧ electric field area
1012‧‧‧Quartz baffle
1013‧‧‧Substrate
1014‧‧‧Substrate base
1016‧‧‧Quartz shell
1017‧‧‧Vacuum pump
1018‧‧‧ scrubber
1019‧‧‧Party screening program
1101‧‧‧Substrate processing chamber
1102‧‧‧ Carrier gas source
1104‧‧‧Carrier supply valve
1106‧‧‧RF power source
1108‧‧‧ Piezoelectric transducer
1110‧‧‧ aerosol generator
1111‧‧‧ chamber inlet valve
1112‧‧‧Top electrode
1113‧‧‧Substrate
1114‧‧‧ bottom electrode
1116‧‧‧ bottom electrode
1118‧‧‧Vacuum pump
1120‧‧‧ scrubber
1201‧‧‧Substrate processing chamber
1202‧‧‧ Carrier gas source
1204‧‧‧ Piezoelectric Transducer
1206‧‧‧ Liquid precursors
1210‧‧‧ aerosol generator
1212‧‧‧ entrance plate
1213‧‧‧Inlet insulator
1214‧‧‧First electrode
1215‧‧‧Substrate
1216‧‧‧Substrate base
1218‧‧‧second electrode
1219‧‧‧Export insulator
1220‧‧‧Export plate
1222‧‧‧Vacuum pump
1511‧‧‧large droplets
1521‧‧‧ Carrier fluid
1531‧‧‧Evaporation precursor
1541‧‧‧film
1551‧‧‧Substrate
2101‧‧‧Substrate processing system
2102‧‧‧Loading lock chamber
2104‧‧‧ Robot arm
2106‧‧‧Maintained area
2108a‧‧‧Substrate processing chamber
2108b‧‧‧Substrate processing chamber
2108c‧‧‧Substrate processing chamber
2108d‧‧‧Substrate processing chamber
2108e‧‧‧Substrate processing chamber
2108f‧‧‧Substrate processing chamber
2110‧‧‧second robot arm

A further understanding of the nature and advantages of the disclosed embodiments can be implemented with reference to the remainder of the specification and the drawings.

FIG. 1 shows a flow chart of a film formation process in accordance with an embodiment.

2 shows a flow chart of a film forming process in accordance with an embodiment.

3A is a side view of a patterned substrate after selective deposition of a self-assembled monolayer, in accordance with an embodiment.

3B is a side view of a patterned substrate after selective deposition using a self-assembled monolayer, in accordance with an embodiment.

3C is a side view of a patterned substrate after removal of a self-assembled monolayer, in accordance with an embodiment.

3D is a side view of a patterned substrate after selective deposition of a self-assembled monolayer, not disclosed herein.

4 shows a diagram of contact angles for a material without and with a self-assembled monolayer, in accordance with an embodiment.

FIG. 5A shows a cross-sectional schematic view of a substrate processing chamber in accordance with an embodiment.

FIG. 5B illustrates a cross-sectional schematic view of a substrate processing chamber in accordance with an embodiment.

FIG. 5C illustrates a cross-sectional schematic view of a substrate processing chamber in accordance with an embodiment.

Figure 6 shows a schematic control diagram of a deposition technique comprising a method according to an embodiment.

FIG. 7 illustrates a top view of an exemplary substrate processing system in accordance with an embodiment.

In the drawings, like components and/or features may have the same reference numerals. In addition, various components of the same type may be distinguished by the addition of a dash after the reference mark and a second reference mark that distinguishes similar components. If only the first reference mark is used in this specification, the description applies to any of the similar components having the same first reference mark, regardless of the second reference mark.

Domestic deposit information (please note according to the order of the depository, date, number)

Foreign deposit information (please note in the order of country, organization, date, number)

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1001‧‧‧Substrate processing chamber

1002‧‧‧ carrier gas source

1003-1‧‧‧ aerosol generator

1003-2‧‧‧ aerosol generator

1004-1‧‧‧Piezoelectric transducer

1004-2‧‧‧Embedded transducer

1005‧‧‧ top cover

1015-1

1015-2

1006‧‧‧ chamber body

1007‧‧‧DC power supply

1008‧‧‧Insulator

1009‧‧‧Top electrode

1010‧‧‧ bottom electrode

1011‧‧‧ electric field area

1012‧‧‧Quartz baffle

1013‧‧‧Substrate

1014‧‧‧Substrate base

1016‧‧‧Quartz shell

1017‧‧‧Vacuum pump

1018‧‧‧ scrubber

1019‧‧‧Party screening program

Claims (20)

A substrate processing chamber for forming a film on a substrate, the substrate processing chamber comprising: a carrier gas source; an aerosol generator configured to receive from the heated carrier gas source a heated carrier gas and configured to generate aerosol droplets from a condensate precursor; a precursor conduit configured to receive the aerosol droplets; a DC power source; An electrode and a second electrode, the first electrode and the second electrode being configured to receive a DC voltage from a DC power source, wherein the first electrode and the second electrode are parallel, and at the first electrode and the Forming a gap between the second electrodes, and wherein the DC voltage is applied between the first electrode and the second electrode to reduce the size of the aerosol droplets, and wherein the first electrode and the The DC voltage between the second electrodes forms an electric field, the electric field is directed from the first electrode to the substrate and directly directed to the second electrode; a substrate pedestal disposed on a substrate in the chamber within the area Wherein the base substrate is configured to support the substrate during processing of the film. The substrate processing chamber of claim 1, wherein the DC voltage is selected to form an electric field having a magnitude between 500 V/cm and 20000 V/cm. The substrate processing chamber of claim 1 wherein the differential voltage is between 100 volts and 2 kilovolts. The substrate processing chamber of claim 1, wherein the first electrode and the second electrode are level. The substrate processing chamber of claim 1, wherein the substrate is parallel to both the first electrode and the second electrode. The substrate processing chamber of claim 1, wherein the substrate is disposed between the first electrode and the second electrode. The substrate processing chamber of claim 1, wherein the piezoelectric transducer is in direct contact with the condensate precursor. The substrate processing chamber of claim 1, wherein the condensate precursor is a liquid precursor. The substrate processing chamber of claim 1, wherein the condensate precursor is formed by dissolving a solid precursor in a solvent. The substrate processing chamber of claim 1, wherein the substrate is perpendicular to both the first electrode and the second electrode. The substrate processing chamber of claim 1, wherein the gap is configured to receive the aerosol droplet directly from the precursor conduit without passing the aerosol droplet through the first electrode or the second electrode . The substrate processing chamber of claim 1, wherein the gap is configured to receive the aerosol droplets through the apertures in the first electrode or the second electrode. A method of processing a layer on a substrate, the method comprising: placing the substrate in a substrate processing region of a substrate processing chamber; dissolving a solid precursor in a solvent for use in an aerosol generator Forming a precursor solution; passing a carrier gas stream into the aerosol generator for generating aerosol droplets; applying an electric field to the aerosol droplets; flowing the aerosol droplets into the substrate processing region And etching the layer on the substrate by chemical reaction with the aerosol droplets. The method of claim 13, wherein the layer consists of two elements. The method of claim 13 further comprising flowing a second precursor into the substrate processing region to remove a single layer from the layer. The method of claim 13 wherein the electric field is a DC electric field having an electric field directed to the substrate. The method of claim 13, wherein the electric field has a value between 500 V/cm and 20000 V/cm. A method of forming a layer on a substrate, the method comprising: placing the substrate in a substrate processing region of a substrate processing chamber; placing a liquid precursor into an aerosol generator; The aerosol generator for generating aerosol droplets; applying an electric field to the aerosol droplets; flowing the aerosol droplets into the substrate processing region; and extracting the aerosol from the substrate Droplets are used to form the layer. The method of claim 18, wherein the layer is a self-organizing single layer (SAM). The method of claim 18, wherein the self-assembled monolayer is selectively formed on the exposed copper portion of the substrate without being formed on the exposed dielectric portion of the substrate, and the method is further included in the method A selectively deposited dielectric is formed on the exposed portions of the dielectric rather than on the exposed portions of copper that are blocked by the self-assembled monolayer.