TWI745311B - 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

The embodiments described herein relate to chemical vapor deposition using low vapor pressure precursors.

The formation of a thin film on the substrate by the chemical reaction of 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). PECVD uses plasma in combination with traditional CVD technology. CVD and PECVD dielectric layers can be used as different layers in semiconductor components. For example, the dielectric layer can be used as an intermetal dielectric layer between conductive lines in the device or interconnects. Alternatively, the dielectric layer can be used as a barrier layer, etch stop layer or spacer, among other layers.

Chemical precursors have been introduced into the substrate processing area of the substrate processing chamber. The substrate is positioned within the substrate processing area, and one or more precursors can be introduced into the substrate processing area to deposit a thin film. The liquid precursor can be used in the following way: the carrier gas is "bubble" through the liquid to carry the vapor into the substrate processing area. 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 the delivery of precursors to the substrate processing area, however, droplet size can adversely affect deposition uniformity and gap filling capabilities.

There is a need for methods for reducing droplet size in aerosol-assisted CVD to broaden the available applications that can utilize low vapor pressure precursors.

Describes systems and methods for processing thin films on the surface of a substrate. The system has an aerosol generator that forms droplets from condensed substances (liquid or solid) of one or more precursors. The carrier gas flows through the condensed substance and pushes the droplets to the substrate placed in the substrate processing area. An inline mechanical pump connected 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 conductive plates, which are configured to pass the droplets between the two conductive plates. 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 droplet enters the substrate processing area and chemically reacts with the substrate to deposit or etch a thin film.

The embodiments described herein include a device for forming a self-assembled monolayer on a substrate. The device includes a source of heated carrier gas. The device further includes an aerosol generator configured to receive heated carrier gas from the heated carrier gas source and configured to generate aerosol droplets from a condensed substance precursor. The device further includes a precursor conduit configured to receive the aerosol droplet. The device further includes a DC power supply. 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 droplet. With vacuum electrical feedthrough, the top electrode and the bottom electrode are biased with a differential voltage from the DC power supply. The differential voltage is applied between the top electrode and the bottom electrode to reduce the size of the aerosol droplet. The device further includes a substrate susceptor, the substrate susceptor being disposed in a substrate processing area in the chamber. The substrate base is configured to support the substrate during the formation of the self-assembled monolayer.

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

The embodiments disclosed herein include substrate processing apparatuses. The substrate processing apparatus includes a substrate susceptor, and the substrate susceptor is disposed in a substrate processing area in the substrate processing apparatus. The substrate base 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 a 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 supply. 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 power 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 reduce the size of the aerosol droplet. The size of the aerosol droplet is maintained between 3 nm and 75 nm until the aerosol droplet reaches the substrate.

The liquid precursor may include octyl phosphoric acid (CH ₃ (CH ₂ ) ₆ CH ₂ -P(O)(OH) ₂ ), perfluorinated octyl phosphoric acid (CF ₃ (CF ₂ ) ₅ CH ₂ -CH ₂ -P(O)(OH) ₂ ), octadecyl phosphonic acid (CH ₃ (CH ₂ ) ₁₆ CH ₂ -P(O)(OH) ₂ ), decyl phosphonic acid, mesityl phosphonic acid, ring One or more of hexylphosphonic acid, hexylphosphonic acid or butylphosphonic acid. The first electrode and the second electrode may be horizontal. The substrate may 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 the solid precursor in a solvent. The substrate may be perpendicular to both the first electrode and the second electrode. The substrate base may be an electrical insulator.

The 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 heated carrier gas from a heated carrier gas source and configured to generate aerosol droplets from a condensed substance 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 supply. The substrate processing chamber further includes a first electrode and a second electrode 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 droplet. The DC voltage applied between the first electrode and the second electrode forms an electric field, and the electric field is directed from the first electrode to the substrate and directly to the second electrode. The substrate processing chamber further includes a substrate susceptor, and the substrate susceptor is disposed in a substrate processing area in the chamber. The substrate base is configured to support the substrate during processing of the film.

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

Embodiments of the present invention include a method of forming a layer on a substrate. The method includes placing the substrate in a substrate processing area of a substrate processing chamber. The method further includes placing the liquid precursor into the aerosol generator. The method further includes flowing a carrier gas into the aerosol generator to generate 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 area. The method further includes forming the layer from the aerosol droplets on the substrate.

The layer may be one of group II-VI or group III-V semiconductors. 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 metal elements. The electric field may be a DC electric field having an electric field directed to the substrate. The method may further include flowing a second precursor into the substrate processing area to form a monolayer on the layer. The electron temperature in the substrate processing area during the formation of the layer may be lower than 0.5 eV.

Embodiments of the present invention include methods of processing layers on a substrate. The method includes placing the substrate in a substrate processing area of a substrate processing chamber. The method further includes dissolving the solid precursor in a solvent to form a precursor solution in the aerosol generator. The method further includes flowing a carrier gas into the aerosol generator to generate 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 area. The method further includes etching the layer on the substrate by a chemical reaction with the aerosol droplets.

The layer may consist of only two elements. The layer may be composed of group III elements and group V elements. The layer may be composed of group II elements and group VI elements. The method may further include flowing a second precursor into the substrate processing area to remove a single layer from the layer. The electric field may be a DC electric field having an electric field directed to the substrate. The electric field may have an amplitude between 500 V/cm and 20000 V/cm. The aerosol droplets may have a diameter between 3 nm and 75 nm. The electron temperature in the substrate processing area during the etching of the layer may be lower than 0.5 eV.

Additional embodiments and features are partially clarified in the following description, and part of them will become obvious to those skilled in the art after consulting this specification, or can be understood by practicing the disclosed embodiments. The features and advantages of the disclosed embodiments can be realized and achieved by means of the means, combinations and methods described in this specification.

Describes systems and methods for processing thin films on the surface of a substrate. The system has an aerosol generator that forms droplets from condensed substances (liquid or solid) of one or more precursors. The carrier gas flows through the condensed substance and pushes the droplets to the substrate placed in the substrate processing area. An in-line mechanical pump connected 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 conductive plates, which are configured to pass the droplets between the two conductive plates. 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 droplet enters the substrate processing area and chemically reacts with the substrate to deposit or etch a thin film.

It is desirable to broaden the set of available chemical precursors that can be used in, for example, CVD, atomic layer etching (ALEt) and atomic layer deposition (ALD) chambers. Low vapor pressure solid precursors and high boiling point 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. Improving the delivery of solids 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 particularly benefit from the use of low vapor pressure precursors. Compared with liquid deposition processes, semiconductor thin film formation applications benefit more from dry deposition processes (vapor phase).

The embodiments described herein may involve solid precursors and/or liquid precursors with low vapor pressure. Liquids and solids (or combinations of them) can generally be described as condensed substances. The condensed substance is composed of atoms/molecules that are always affected by the force exerted by neighboring atoms/molecules, and can be defined as a substance having substantially no or no mean free path according to the embodiment. In an embodiment, a solid precursor with a low vapor pressure can be dissolved in a single solvent or a mixture of compatible solvents, and this combination can be referred to as a condensed substance. Aerosols are formed from condensed substances and can be formed using ultrasonic humidifiers. Ultrasonic humidifiers may have piezoelectric transducers that can operate at one or more frequencies. The ultrasonic humidifier can generate aerosol droplets, and use a carrier gas such as nitrogen (N ₂ ) or argon (Ar) to carry the aerosol droplets into the reaction chamber (substrate processing area). The carrier gas can be inert, and neither forms a covalent chemical bond with the condensed substance nor with the substrate. An in-line mechanical pump connected to the aerosol generator can also be used to push the droplets towards the substrate.

The aerosol droplets can pass through conduits that are heated to prevent condensation or contribute to a reaction with the substrate after the aerosol droplets enter the substrate processing area. The substrate processing area is inside the substrate processing chamber, and is a vacuum chamber that evacuates atmospheric gas before the precursor is delivered into the substrate processing area. In an embodiment, the substrate processing area is sealed to isolate the external atmosphere, and can be operated at a pressure much lower than the atmospheric pressure, thereby evacuating the atmospheric gas. The condensate precursor need not be volatile to generate aerosol droplets. The precursor of the condensed substance can be dissolved in a solvent or a mixture of solvents, from which aerosol droplets are generated. Thanks to the embodiments described herein, a wider range of precursors can now be used because volatility is no longer necessary. The substrate processing chamber can also be equipped with two electrodes that can generate an electric field. It has been found that the electric field can reduce the size of the aerosol droplet or maintain the smaller size of the aerosol droplet as desired.

In order to better understand and understand the embodiments described herein, reference is now made to FIGS. 1 and 2. FIGS. 1 and 2 are flowcharts of the film forming processes (101 and 201) according to the embodiments. Reference will be made to FIG. 5A at the same time, which includes a schematic cross-sectional view of a substrate processing chamber 1001 according to an embodiment. Any one of the substrate processing chambers of FIG. 5A, FIG. 5B, and FIG. 5C or a combination of their components may be used to perform the process described herein (for example, 101 or 102). In the process 101, in operation 110, the substrate 1013 is delivered to the substrate processing area of the substrate processing chamber 1001. The substrate 1013 is supported by a substrate susceptor 1014, which can be resistively heated and/or cooled by passing a thermally controlled liquid through the substrate susceptor 1014. A part of the substrate susceptor and the entire substrate 1013 are shown as being within the substrate processing area. The substrate processing area is additionally bounded by a quartz baffle 1012 and a quartz housing 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 put into the aerosol generator 1003-1 with the piezoelectric transducer 1004-1. In operation 130, the carrier gas is heated in the heated carrier gas source 1002, and the carrier gas flows 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). In addition, in operation 140, the aerosol droplets flow through the precursor conduit 1015-1 and enter the substrate processing chamber 1001 through the top cover 1005. Before entering the substrate processing area containing the substrate 1013, the aerosol droplets also flow through the top electrode 1009, 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 aerosol droplets pass between the two electrodes (operation 150). The electric field is applied in the electric field region 1011 and directed from the top electrode 1009 to the bottom electrode 1010. The insulator 1008 is configured to maintain electrical separation between the top electrode 1009 and the bottom electrode 1010. In an embodiment, the chamber body 1006 and the top cover 1005 may also be electrically insulated from one or both of the top electrode 1009 and the bottom electrode 1010. The DC voltage difference is generated in the DC power supply 1007 and is introduced into the substrate processing area by means of a vacuum compatible electric feedthrough. In an embodiment, the aerosol droplet size is reduced or maintained by applying a DC electric field perpendicular to the main plane of the substrate 1013. The top electrode 1009 and the bottom electrode 1010 have perforations that allow aerosol droplets to pass through them, but both of them are flat, and each is parallel to the main plane of the substrate 1013. The substrate can also be electrically biased during the deposition process. In operation 160, a thin film is deposited from aerosol droplets on the substrate 1013, and in operation 170, the substrate is removed from the substrate processing area.

The aerosol generator 1003 can be positioned close to the substrate processing chamber 1001 to further maintain a small aerosol droplet size. The volume in the aerosol generator 1003 may be roughly proportional to the area of the substrate to be processed. For example, for a 300 mm substrate, one liter of aerosol generator 1003 can be used to generate aerosol droplets. A mass flow controller can be used to control the flow rate of the aerosol droplets in 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 to maintain a small aerosol droplet size.

For the film forming process 101, solid precursors have been used. In embodiments, solid or liquid precursors may have been used, and the solid precursors exemplarily exhibit technical effectiveness in accommodating low vapor pressure precursors. In the following example, a liquid precursor is used, but in an embodiment, a solid precursor can replace the liquid precursor. In operation 210, the substrate is placed in the substrate processing area.

The liquid precursor is put into an aerosol generator 1003-2 with an embedded transducer 1004-2. The carrier gas is heated in the heated carrier gas source 1002, and the carrier gas flows 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 the 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 enter the substrate processing chamber 1001 through the top cover 1005. In operation 230, before entering the substrate processing area containing the substrate 1013, the aerosol droplets then flow through the top electrode 1009 and flow through the bottom electrode 1010. Before entering the substrate processing area, a DC electric field is applied between the top electrode 1009 and the bottom electrode 1010, while aerosol droplets pass between the two electrodes. The electric field is applied in the electric field region 1011 and directed from the top electrode 1009 to the bottom electrode 1010. The insulator 1008 is configured to maintain electrical separation between the top electrode 1009 and the bottom electrode 1010. The DC voltage difference is generated in the DC power supply 1007 and is introduced into the substrate processing area by means of a vacuum compatible electric feedthrough. In an embodiment, the aerosol droplet size is reduced or maintained by applying a DC electric field perpendicular to the main plane of the substrate 1013. The top electrode 1009 and the bottom electrode 1010 have one or more perforations that allow aerosol droplets to pass through the two, but the two are also planar, and each is parallel to the main plane of the substrate 1013. In an embodiment, the susceptor may 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 area can be evacuated to remove unreacted aerosol droplets and reaction byproducts. The second precursors with different chemical characteristics are then flowed into the substrate processing area (operation 240) to complete the formation of the "atomic" layer deposition 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 area. In general, the precursors can be delivered to the substrate processing area in a sequential, alternating manner, as in the examples, or, depending on the embodiment, they can enter the reactor at the same time. In an embodiment, the precursors can be combined with each other before entering the substrate processing area.

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

In all of the embodiments described herein, the precursor is in a phase of condensed matter, which may include dissolution in a solvent. In an embodiment, the vapor pressure of the condensed material precursor before dissolution (or if no solvent is used at all) may be zero, low to unmeasurable, less than 10 Torr, less than 20 Torr, or less than 30 Torr. According to embodiments, after dissolution, the vapor pressure of the solution containing the condensed substance precursor and a suitable solvent may be 10 Torr, less than 30 Torr, or less than 50 Torr. Exemplary condensate precursors will be presented after the introduction of a motivating deposition application.

An exemplary deposition application that can benefit from the techniques and hardware described herein is the formation of self-assembled monolayers, which can involve the use of low vapor pressure liquid precursors. The benefit of the deposition process described herein is to finely and complexly pattern the extremely conformal deposition rate on the substrate. Deeper gaps, trenches or vias often exhibit higher deposition rates near their openings than the deeper parts of the trenches, especially when the droplet size is larger than the feature size or line width when. According to embodiments, the methods described herein can be used to deposit conformal with 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 etching rate, no matter how complex the patterning on the patterned substrate is. In an embodiment, the width and depth of the via or trench (feature) may be between 3 nm and 20 nm or between 5 nm and 10 nm. All the parameters described herein are applicable to both etching and deposition, but the illustrative example describes the deposition process. In an embodiment, the width of the via or trench (in a narrower dimension) may be less than 30 nm, less than 20 nm, or less than 10 nm. Depth is measured here from the top to the bottom of the trench. "Top", "above" and "upward" will be used herein to describe portions/directions that are vertically away from the plane of the substrate and further away from the main plane of the substrate in the vertical direction. "Vertical" will be used to describe objects that are aligned in the "upward" direction toward the "top". Other similar terms can also be used, and their meaning will now be clear.

Exemplary low vapor pressure precursors include precursors 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, but illustrative examples can be helpful in understanding the embodiments disclosed herein. The precursor used to deposit the self-assembled monolayer may have a tail moiety (TM) that is chemically distinguished from the head moiety (HM). HM has been found to contribute to the formation of the 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 condensable substance precursor may include octyl phosphoric acid (CH ₃ (CH ₂ ) ₆ CH ₂ -P(O)(OH) ₂ ), perfluorinated octyl phosphoric acid (CF ₃ (CF ₂ ) ₅ CH ₂ -CH ₂ -P(O)(OH) ₂ ), octadecyl phosphonic acid (CH ₃ (CH ₂ ) ₁₆ CH ₂ -P(O)(OH) ₂ ), decyl phosphonic acid, three One or more of tolylphosphonic acid, cyclohexylphosphonic acid, hexylphosphonic acid or butylphosphonic acid.

The tail portion (TM) can prevent or hinder the formation of a thin film on the patterned layer during subsequent exposure to the second deposition precursor. According to embodiments, the tail portion of the phosphoric acid precursor may include 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 an alternative to much smaller hydrogen atoms seems to hinder patterned layer nucleation. In an embodiment, the tail portion of the phosphoric acid precursor may 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 embodiments, TM may include 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 .

The precursor used to deposit a self-assembled monolayer (SAM) can provide a head portion that is covalently bonded to the substrate, and a tail portion that extends away from the substrate from the covalent bond. The tail portion includes a relatively long sequence of covalent bonds called a chain. 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 contain sulfur-containing groups, such as thiol groups. According to embodiments, the precursor may be methyl mercaptan (CH ₃ SH), ethyl mercaptan (C ₂ H ₅ SH) or butane 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 an embodiment, 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 (CF ₃ (CH ₂ ) _n SH) where n is 9-15. According to an embodiment, the head group may include a nitrogen-containing group. In an embodiment, the precursor may be 3-aminopropyltriethoxysilane (APTES), (3-aminopropyl)trimethoxysilane ((3-Aminopropyl)trimethoxysilane, APTMS), 1,3 diamino One or more of propane, ethylenediamine, ethylenediaminetetraacetic acid, diethylamine, and methylamine.

The rate of film deposition on the patterned layer on the SAM can be much lower than the rate of film deposition on the portion not covered by the self-assembled monolayer. The rate of film deposition on SAM can be reduced due to the presence of SAM, and this deposition rate can be much lower than if SAM does not exist. In an embodiment, the rate of deposition on the SAM-free portion 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 parts on the patterned substrate. For example, the deposition rate of SAM can be easily performed on the exposed metal part, but not on the exposed dielectric part of the patterned substrate. The metal part may be conductive, and may contain or consist of an element that forms a conductive material in the state of a condensed substance (if no other elements are present). In an embodiment, the deposition rate of the SAM layer on the exposed metal portion may exceed the deposition rate on the exposed dielectric portion by 10, 15, 20, or 25 times.

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

The self-assembled monolayer (SAM) as grown here can be selectively deposited on some parts of the patterned substrate, but not on other parts. Then, subsequent deposition can be performed on the area without the SAM coating. Compared with traditional methods involving lithographic patterning, the method described herein can save costs and improve overlay accuracy. After the selective deposition of the SAM, the subsequent deposition may also be referred to as selective deposition, but the subsequent deposition is a reverse image of the selectively deposited SAM layer. Subsequent deposition of the film can have greater utility in the operation of the completed integrated circuit or in other processing (compared to SAM). 3A, 3B, and 3C are side views of the patterned substrate at certain points during or after the selective deposition of the self-assembled monolayer 310 and the selectively deposited dielectric 315-1. In FIG. 3A, the self-assembled single layer 310 is deposited on the exposed copper 305 in the gaps in the patterned substrate 301, but not on other exposed parts. The exposed copper 305 may be bare, that is, there may be no liner layer or barrier layer between the top of the copper 305 and the self-assembled single layer 310.

FIG. 3B shows a selectively deposited dielectric 315-1 formed at a location without a self-assembled monolayer, in the example, anywhere other than copper. Each self-assembled monolayer 310 can be removed to leave the selectively deposited dielectric 315-1, with the exception of the embedded copper 305 in the gaps of the patterned substrate 301, as shown in FIG. 3C. FIG. 3D is a side view of the patterned substrate after selectively depositing a self-assembled monolayer of an embodiment not disclosed herein. The prior art method of forming a self-assembled monolayer has been tested using the process flow of FIGS. 3A-3C, and tends to produce a selectively deposited dielectric 315-2. This selectively deposited dielectric 315- 2 Cover all parts of the embedded copper 305, and increase the resistivity in the finished component or cause the finished component to fail.

FIG. 4 shows a graph of contact angles of materials without and with adsorbed self-assembled monolayers according to an embodiment. The contact angle is measured on each surface by wetting the surface with deionized water and observing the angle formed by the water acting on various materials. Silicon oxide, low-k dielectrics, copper, and titanium nitride are characterized to measure the contact angle, and four materials are shown from left to right. Each dotted rectangle in Figure 4 represents one of the four materials and contains two measurements: one measurement is from a bare surface, and one measurement is after exposure to octadecylphosphonic acid (known as ODPA) . Only copper showed a statistically significant difference between the bare surface and the surface exposed to octadecylphosphonic acid. The lack of difference between the exposed surface and the exposed surface proves that octadecylphosphonic acid is not chemisorbed to each of silicon oxide, low-k dielectric, and titanium nitride. In an embodiment, the self-assembled single layer may be formed on some parts (for example, copper) of the patterned substrate, but not on another part. According to the embodiment, then, subsequent deposition may be performed only on the area without the SAM coating.

According to embodiments, exemplary solvents that can be used to dissolve the precursors of low vapor pressure condensable substances may include isopropanol (IPA), 1-butanol, toluene, xylene, benzene, hexane, cyclohexane, tetrahydrofuran, two One or more of formazan, dimethylformamide, acetonitrile, dichloromethane, ethyl acetate and chloroform. In an embodiment, the solvent may include aromatic hydrocarbons, may include carbon and hydrogen, or be composed of carbon and hydrogen, or may include carbon, hydrogen, and oxygen, or be composed of carbon, hydrogen, and oxygen.

FIG. 5A shows a schematic cross-sectional view of a substrate processing chamber according to an embodiment, which may be used to perform the aforementioned method. The substrate temperature can rise above room temperature during the deposition process, depending on the type of film grown. The dry process described in this article enables the process to be performed at a higher temperature than the prior art liquid process. Smaller aerosol droplets can leave the hole of the quartz baffle 1012, and then approach and contact the substrate 1013, while the substrate is maintained between 100°C and 800°C, between 200°C and 700°C, and at 300°C Temperature between 600°C and 400°C or between 400°C and 500°C. These substrate temperatures can be present in all deposition operations described herein. The chamber body 1006 and/or the top cover 1005 may be stainless steel (for example, SST 304 or preferably SST 316) material, which can withstand relatively high temperatures (possibly up to 400°C) while maintaining the quartz baffle 1012/quartz The vacuum integrity between the substrate processing area in the housing 1016 and the atmosphere outside the chamber body 1006 and the top cover 1005. The chamber body 1006, the top cover 1005 and any other components can be sealed with O-rings, which are compatible with a specific process environment to ensure gas between the substrate processing area and the atmosphere outside the substrate processing chamber 1001 isolation.

The chamber main body 1006 and/or the top cover 1005 may be cooled by flowing a coolant through a coolant channel formed or formed by, for example, stainless steel. The coolant channel can be located near the O-ring connector to prevent the O-ring from being exposed to high temperatures. In order to safely or reduce the base pressure in the quartz baffle 1012 and the quartz housing 1016 (substrate processing area), the temperature of the top cover 1005 and/or the chamber body 1006 can be maintained below 70° C. during the film formation. The presence of the quartz baffle 1012 and the quartz housing 1016 can further reduce the operating temperature of the top cover 1005 and/or the chamber body 1006. The quartz baffle 1012 (for example, a porous quartz part), the top electrode 1009, and/or the bottom electrode 1010 can be kept below 100° C. during film formation. The substrate susceptor 1014 can be heated to the previously given desired temperature of the substrate 1013, and the temperature of the substrate 1013 can be maintained at a level conducive to the process. The substrate base 1014 is vertically adjustable to provide flexibility in positioning the substrate 1013 relative to the bottom of the quartz baffle 1012. The thermocouple may be attached to the top cover 1005 and/or the chamber body 1006 or embedded in the top cover 1005 and/or the chamber body 1006 to provide feedback control of temperature and/or coolant flow. Thermocouples can also be used to stop the flow of precursors and also stop heating the substrate base 1014 when the safe temperature upper limit set point is exceeded.

In an embodiment, the pressure in the substrate processing area 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 may proceed thermally, only excited by the temperature of the substrate itself. In embodiments that rely on the temperature of the substrate to achieve the deposition reaction, the term "plasma-free" may be used herein to describe the substrate processing area during applications where plasma power is not or substantially not used. The lack of plasma in the substrate processing area 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 appropriate reactions to proceed. In an embodiment, the plasma power applied to the substrate processing area may be less than 100 watts, less than 50 watts, less than 30 watts, less than 10 watts, and may be 0 watts.

Any lack of local plasma (or reduction in magnitude) is satisfactory in making the deposition process more conformal and less likely to deform features. The term "plasma-free" will be used herein to describe a substrate processing area during which plasma power is not applied or substantially not applied to the substrate processing area. On the other hand, according to an embodiment, the electron temperature in the substrate processing region may 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 remote plasma before entering the substrate processing area. For example, it exists in the remote plasma region or a separate chamber region and is used to direct aerosol droplets to the substrate processing region and any remote region may be plasma-free as defined herein.

A gap (shown as an electric field region 1011 in FIG. 5A) exists between the top electrode 1009 and the 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 small aerosol droplet size can 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 DC voltage of negative potential with respect to the top electrode 1009. According to embodiments, the magnitude of the DC voltage difference may 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 a value between 500 V/cm and 20000 V/cm, between 1000 V/cm and 10000 V/cm, or between 2000 V/cm Amplitude between and 7000 V/cm. According to embodiments, it has been found that the application of a DC electric field will reduce smaller diameter droplets, or maintain their size, even when the aerosol droplets are uncharged and non-polar.

The additional benefits of the hardware and process described herein will now be described. Prior art aerosol droplets already have a diameter between about 0.5 μm and a few μm. Due to the presence of larger diameter droplets that deliver the precursor to the substrate, several problems arise. According to embodiments, 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 facilitates penetration of the precursor source into smaller features on the patterned substrate. The smaller size can result in enhanced material gap filling and fewer trapped voids in the gap. The smaller size also enables 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 enables the elements present in the low vapor pressure precursors (and solvents if solvents are used) to be released more quickly. Some elements are undesirable in the deposited film. The smaller droplet sizes described herein allow undesirable elements (for example, carbon or hydrogen) to form volatile substances that are easily detached from the surface during the deposition reaction. Additional benefits include reduced surface roughness and reduction in the number and size of grain boundaries that are achieved using the techniques described herein.

Ultrasonic agitation may be used to generate smaller aerosol droplets in the aerosol generator 1003. As described above, the size of the aerosol droplets can be reduced by applying a DC electric field in the electric field region 1011 before the aerosol droplets enter the substrate processing area (or their growth is prevented). 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 enter the substrate processing region. According to embodiments, the particle screening program 1019 may allow aerosol droplets with diameters less than 0.3 μm, less than 0.25 μm, or less than 0.2 μm to pass through, while suppressing or preventing the flow of droplets having diameters greater than these size thresholds. The screening program can be placed at any position along the precursor conduit 1015, including a position directly above the top electrode 1009. In an embodiment, the screening program may be located in the top electrode 1009, may be located in the electric field region 1011, may be located 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 condensation particle counter or detector).

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

The equipment and techniques described herein can be used to etch or form a variety of layers, including metals, semiconductors, and insulators. According to embodiments, these layers may be conformal, and may be self-assembled monolayers (SAM) formed by organic or inorganic molecules or atomic layer deposition (ALD). Merely as illustrative examples, 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 thin film may be a metal oxide, a III-V semiconductor, or a II-VI semiconductor.

Figure 5A shows two aerosol generators (1003-1 and 1003-2) used to deliver low vapor pressure precursors into the substrate processing area. There may be more than two aerosol generators, and they may be enhanced by non-aerosol generating sources, which are not shown in the drawings to increase readability. The transducers in one or more of the aerosol generators can alternatively be left off to equip non-aerosol generating sources with the hardware shown in the figure. During the film growth process, 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 way, n-type or p-type semiconductors (eg, silicon) can be formed using the techniques and hardware described herein.

FIG. 5B shows a schematic cross-sectional view of another substrate processing chamber 1101 according to an embodiment, which may also be used to perform the aforementioned method. The features and elements of each embodiment can be added to some or all of the features and elements of another embodiment to obtain additional embodiments. The substrate 1113 is put into the substrate processing area 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 (for example, ultrasound) to a piezoelectric transducer 1108 that is placed in physical contact with the aerosol generator 1110. The piezoelectric transducer 1108 evaporates the condensed material precursor source (for example, solid or liquid), and the carrier gas from the carrier gas source 1102 flows through the aerosol generator 1110, and passes the evaporated precursor through the chamber inlet valve 1111 is carried to the substrate processing area of the substrate processing chamber 1101. The carrier gas may be heated before 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 from between these electrodes into the substrate processing area. Figure 5A shows an aerosol droplet delivered through one of these electrodes, and Figure 5B shows a configuration that does not need to flow through the electrode. The DC power supply (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 precursor vaporized in the substrate processing area. The electric field is directed from the top electrode 1112 to the bottom electrode 1114. An electrical insulator is provided 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 can be applied to the top electrode 1112 and the bottom electrode 1114 using a vacuum feedthrough, or directly to these electrodes, without first passing through the vacuum. In an embodiment, the aerosol droplet size is reduced or maintained by applying a DC electric field perpendicular to the substrate 1113. In an embodiment, the top electrode 1112 and the bottom electrode 1114 are planar, and are each parallel to the main plane of the substrate 1113. The substrate can be electrically biased during the deposition process. A thin film is deposited on the substrate 1113 from aerosol droplets. Unreacted precursors or other process effluents can be pumped out using a vacuum pump 1118, and the scrubber 1120 can be used to make process effluents chemically modified to improve environmental compatibility.

The heater coil 1116 may be provided on the top electrode 1112 and/or the bottom electrode 1114. Heating the top electrode 1112 and/or the bottom electrode 1114 prevents condensation of evaporated precursors and further reduces droplet size. The substrate temperature can rise above room temperature during the deposition process, depending on the type of film grown. The dry process described in this article enables the process to be performed at a higher temperature than the prior art liquid process. 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. The process pressure is also given before, and for the sake of brevity, it will not be repeated here. According to the embodiment, the reaction can proceed thermally, only excited by the temperature of the substrate itself. The substrate processing area can be described as free of plasma, and its definition has been presented previously. 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 shown.

FIG. 5C shows a schematic cross-sectional view of another substrate processing chamber 1201 according to an embodiment, which may also be used to perform the aforementioned method. The features and elements of each embodiment can be added to some or all of the features and elements of another embodiment to obtain additional embodiments. The substrate 1215 is placed in the substrate processing area of the substrate processing chamber 1201 before deposition. The substrate 1215 is supported on the substrate base 1216. The substrate base 1216 may be a vacuum compatible material, and in an embodiment, an electrical insulator. The substrate susceptor 1216 may be further configured to be vacuum compatible at the substrate temperature described herein. In an embodiment, the substrate base 1216 may be a carbon block, and may contain or consist of carbon. The carrier gas flows into the aerosol generator 1210 from the carrier gas source 1202 and penetrates the liquid precursor 1206 in a foaming manner. The RF power source (not shown) is configured to supply an alternating current signal (for example, ultrasound) to the piezoelectric transducer 1204 provided inside the aerosol generator 1210. The piezoelectric transducer 1204 can vibrate to beneficially facilitate the carrying of the aerosol droplets of the liquid precursor 1206 toward the substrate processing area of the substrate processing chamber 1201.

In this particular embodiment, the electrodes are aligned vertically. The first electrode 1214 is also parallel to the second electrode 1218, and the evaporated precursor or aerosol droplets are delivered through the first electrode 1214 into the substrate processing area between the two electrodes. Fig. 5A shows an aerosol droplet delivered through one of these electrodes, and Fig. 5C shows a configuration with this common property. The 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 precursor vaporized in the substrate processing area. The 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 plate 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 plate 1212. Similarly, the outlet plate 1220 can be electrically isolated from the second electrode 1218 by inserting an outlet insulator 1219 between the second electrode 1218 and the outlet plate 1220. In an embodiment, the DC voltage difference is generated within the DC power source and can be applied to the first electrode 1214 and the second electrode 1218 using a vacuum feedthrough, or directly applied to these electrodes without first passing through the vacuum. Compared with each of the embodiments depicted in FIG. 5A and FIG. 5B, in the embodiment, the aerosol droplet size is reduced or maintained by applying a DC electric field parallel to the substrate 1215. In an embodiment, the first electrode 1214 and the second electrode 1218 are planar, and each is perpendicular to the main plane of the substrate 1215. A thin film is deposited on the substrate 1215 from aerosol droplets. According to embodiments, unreacted precursors or other process effluents may be pumped out through the second electrode 1218, the outlet insulator 1219, and the outlet plate 1220. The process effluent can be pumped out by the vacuum pump 1222. Substrate temperature, process pressure, electric field strength, droplet size, and process benefits have previously been shown.

Fig. 6 shows a schematic comparison diagram of a deposition technique including a method according to an embodiment. Wet spray pyrolysis, dry spray pyrolysis, aerosol-assisted CVD (the method in this article) and powder spray pyrolysis are presented in Figure 6 and compared. Wet spray pyrolysis and dry spray pyrolysis, aerosol assisted CVD (AACVD) and powder spray pyrolysis may each have the ability to form larger droplets 1511. In the case of dry spray pyrolysis, AACVD and powder spray pyrolysis, the larger droplets 1511 can be separated from the carrier fluid 1521. Various aspects of the devices and methods described herein are used to reduce the size of the droplets and maintain a small 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 individual molecular components. A uniform thin film 1541 is formed on the substrate 1551, while agglomeration is still observed in each of wet spray pyrolysis, dry spray pyrolysis, and powder spray pyrolysis.

The examples discussed so far use low vapor pressure precursors to deposit thin films on the substrate by alternate exposure or continuous exposure. The technique described herein can also be used to perform etching by being exposed to an etching precursor (etchant) having a low vapor pressure in a manner of alternate exposure or continuous exposure. In an embodiment, the low vapor pressure etchant may be a halogen-containing precursor, a fluorine-containing precursor, a chlorine-containing precursor, or a bromine-containing precursor. According to embodiments, the low vapor pressure etchant may be a precursor containing metal and halogen, where the halogen may be fluorine, chlorine, or bromine. Similarly, in an embodiment, the low vapor pressure etchant may be a halide (e.g., alkyl halide). The low vapor pressure etchant may have a long alkyl chain, as described elsewhere herein, which is associated with the low vapor pressure remedied by the techniques presented herein.

In an embodiment, the process described herein may involve removing a single layer each time it is alternately exposed to a first precursor and a second precursor. According to an embodiment, the process described herein may involve the deposition of a single layer of material each time the first precursor and the second precursor are alternately exposed. Both the first precursor and the second precursor may be low vapor pressure precursors prepared by aerosol generation technology. Alternatively, one of the precursors may be a low vapor pressure precursor prepared by aerosol generation technology, while the other may have a relatively high vapor pressure and be delivered to the substrate processing area by simpler traditional means.

In all the embodiments described herein, the low vapor pressure condensable substance precursor (eg, solid precursor or liquid precursor) can be between 5 mgm (milligrams per minute) and 500 mgm, and between 10 mgm and 300 mgm. A flow supply between 25 mgm and 200 mgm occasionally. 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 can 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 the embodiment, compared with the slow deposition rate of the prior art aerosol-assisted chemical vapor deposition, the film growth rate using the aerosol droplet generation method and the hardware described herein can exceed 300 Å/min, which can be Exceed 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 sequential alternate exposures. Generally speaking, during the alternate exposure deposition sequence, all the deposition operations and etching operations of the process described herein can be simply replaced by a stoppage during the flow of the precursor into the substrate processing area. Alternatively, a gas may be used to actively purge the substrate processing area, which gas does not substantially exhibit chemical reactivity to exposed materials on the patterned substrate. After the precursor is stopped or actively purified, the next precursor can flow into the substrate processing area to continue the etching/deposition of the patterned substrate/etching/deposition on the patterned substrate.

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

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

Embodiments of the substrate processing chamber can be incorporated into larger manufacturing systems for the production of integrated circuit wafers. FIG. 7 shows one such substrate processing system (host) 2101 having a deposition chamber, an etching chamber, a baking chamber, and a curing chamber in the embodiment. In this figure, a pair of front opening unified pods (loading lock chamber 2102) supply substrates of various sizes. These substrates are received by the robot arm 2104 and placed in the substrate processing chambers 2108a-f. One of them was previously placed in the low-pressure holding area 2106. The second robotic arm 2110 can be used to transfer substrate wafers from the holding area 2106 to the substrate processing chambers 2108a-f and back. Each substrate processing chamber 2108a-f can be equipped to perform many substrate processing operations, except for loop layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition In addition to deposition (PVD), etching, atomic layer etching, pre-cleaning, degassing, orientation, and other substrate manufacturing processes, the dry etching process described in this article is also included.

As used herein, a "patterned substrate" can be a supporting substrate with or without a layer formed thereon. The patterned substrate may be an insulator or semiconductor with various doping concentrations and distributions, and may be, for example, the type of semiconductor substrate used in the manufacture of integrated circuits. The exposed "metal" of the patterned substrate is mainly metal elements, but may include other elemental components in small concentrations, such as nitrogen, hydrogen, silicon, and carbon. The exposed "metal" may be composed of or substantially composed of metal elements. The exposed "metal nitride" of the patterned substrate is mainly nitrogen and metal elements, but may include other elemental components in small concentrations, such as nitrogen, hydrogen, silicon, and carbon. The exposed "metal nitride" may consist of nitrogen and metal elements or consist essentially of nitrogen and metal elements. Other examples of layers that can be processed according to the methods described herein include titanium oxide, aluminum oxide, zirconium oxide, titanium doped silicon oxide, and hafnium oxide.

The exposed "silicon" or "polysilicon" of the patterned substrate is mainly Si, but may include other elemental components in small concentrations, such as nitrogen, hydrogen, and carbon. The exposed "silicon" or "polysilicon" may consist of silicon or consist essentially of silicon. The exposed "silicon nitride" of the patterned substrate is mainly silicon and nitrogen, but may include other elemental components in small concentrations, such as nitrogen, hydrogen, and carbon. "Exposed silicon nitride" may consist of silicon and nitrogen or consist essentially of silicon and nitrogen. The exposed "silicon oxide" of the patterned substrate is mainly SiO ₂ , but may include other elemental components (such as nitrogen, hydrogen, and carbon) in small concentrations. In some embodiments, the silicon oxide region etched using the method disclosed herein consists essentially of silicon and oxygen.

The carrier gas described herein may be an inert gas. The term "inert gas" refers to any gas that does not form chemical bonds when etching or incorporating a layer. Exemplary inert gases include rare gases, but may also include other gases as long as no chemical bonds are formed when (usually) traces are trapped in the layer.

The gap is an etched geometry with any horizontal aspect ratio. Viewed from above the surface, the gap can be circular, elliptical, polygonal, rectangular, or various other shapes. A "groove" is a long gap. The trench may have the shape of a trench surrounding an island of material, and the aspect ratio is the length or circumference of the trench divided by the width of the trench. "Vias" are short gaps with a standard aspect ratio, which is almost whole when viewed from above. The via can be round, slightly elliptical, polygonal or slightly rectangular. The via hole may be filled with metal or may not be filled with metal to form a vertical electrical connection.

In the case that several embodiments have been disclosed, those skilled in the art will recognize that various modifications, alternative structures, and equivalents can be used without departing from the spirit of the disclosed embodiments. In addition, many well-known processes and components have not been described to avoid unnecessarily obscuring the disclosed embodiments. Therefore, the above description should not be taken as limiting the scope of the claims.

When providing a range of values, it should be understood that every intermediate value between the upper limit and the lower limit of the range (unless the context clearly indicates otherwise, to one-tenth of the lower limit unit) is also exactly disclosed. Covers every smaller range between any stated value or intermediate value in the stated range and any other stated value or intermediate value in this stated range. The upper and lower limits of these smaller ranges can be independently included in or excluded from the range, and any limit value, excluding limit value, or two limit values are included in the smaller range Each range of is also encompassed within the disclosed embodiments, depending on any exactly excluded limit value in the stated range. Where the stated range includes one or two of these limit values, it also includes a range excluding any one or two of those included limit values.

As used herein and in the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. 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.

In addition, the terms "including" and "including" when used in this specification and the appended claims are intended to indicate the presence of stated features, integers, components or steps, but they do not exclude one or more other features, The existence or addition of integers, components, steps, actions, or groups.

101‧‧‧Process 110‧‧‧Operation 120‧‧‧Operation 130‧‧‧Operation 140‧‧‧Operation 150‧‧‧Operation 160 220‧‧‧Operation 230‧‧‧Operation 240‧‧‧Operation 250‧‧‧Operation 260‧‧‧Operation 270‧‧‧Operation 301 315-1‧‧‧Dielectric 315-2‧‧‧Dielectric 1001‧‧‧Substrate processing chamber 1002‧‧‧Carrier gas source 1003-1‧‧‧Aerosol generator 1003-2‧‧‧Gas Sol generator 1004-1‧‧‧Piezoelectric transducer 1004-2‧‧‧Embedded transducer 1005‧‧‧Top cover 1015-1‧‧‧Precursor catheter 1015-2‧‧‧Precursor catheter 1006. ‧‧Substrate base 1016‧‧‧Quartz housing 1017‧‧‧Vacuum pump 1018‧‧‧Scrubber 1019‧‧‧Particle screening program 1101‧‧‧Substrate processing chamber 1102‧‧‧Carrier gas source 1104‧‧‧Carrier Gas 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. Precursor 1210‧‧‧Aerosol generator 1212‧‧‧Entrance plate 1213‧‧‧Entrance insulator 1214‧‧‧First electrode 1215‧‧‧Substrate 1216‧‧‧Substrate base 1218‧‧‧Second electrode 1219‧ ‧‧Export insulator 1220‧‧‧Export plate 1222‧‧‧Vacuum pump 1511‧‧ Large droplet 1521‧‧‧Carrier fluid 1531‧‧Evaporation precursor 1541‧‧‧Film 1551‧‧‧Substrate 2101‧‧‧ Substrate processing system 2102‧‧‧Load gate chamber 2104‧‧‧Robot arm 2106‧‧‧Holding 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 achieved with reference to the rest of the specification and the accompanying drawings.

FIG. 1 shows a flowchart of a film formation process according to an embodiment.

Fig. 2 shows a flow chart of a film forming process according to an embodiment.

Figure 3A is a side view of a patterned substrate after selective deposition of self-assembled monolayers according to an embodiment.

3B is a side view of a patterned substrate after selective deposition using a self-assembled single layer according to an embodiment.

3C is a side view of the patterned substrate after removing the self-assembled single layer according to the embodiment.

Figure 3D is a side view of a patterned substrate after selective deposition of self-assembled monolayers in embodiments not disclosed herein.

Fig. 4 shows a diagram of the contact angle of a material without and with a self-assembled monolayer according to an embodiment.

FIG. 5A shows a schematic cross-sectional view of a substrate processing chamber according to an embodiment.

FIG. 5B shows a schematic cross-sectional view of a substrate processing chamber according to an embodiment.

FIG. 5C shows a schematic cross-sectional view of a substrate processing chamber according to an embodiment.

Fig. 6 shows a schematic comparison diagram of a deposition technique including a method according to an embodiment.

FIG. 7 shows a top view of an exemplary substrate processing system according to an embodiment.

In the drawings, similar components and/or features may have the same reference label. In addition, various parts of the same type can be distinguished by adding a dash after the reference mark and a second reference mark for distinguishing similar parts. If only the first reference sign is used in this specification, the description is applicable to any of the similar components having the same first reference sign, regardless of the second reference sign.

Domestic hosting information (please note in the order of hosting organization, date, and number) None

Foreign hosting information (please note in the order of hosting country, institution, date, and number) None

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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‧‧‧The main body of the chamber

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‧‧‧Particle screening program

Claims (18)

A substrate processing chamber for forming a thin film on a substrate, the substrate processing chamber comprising: a carrier gas source; an aerosol generator configured to receive the heated carrier gas source A heated carrier gas and configured to generate aerosol droplets from a condensed substance precursor; a precursor conduit configured to receive the aerosol droplets; a DC power source; a first Electrodes and a second electrode, the first electrode and the second electrode are configured to receive a DC voltage from the DC power source, wherein the first electrode and the second electrode are parallel, and the first electrode and the second electrode A gap is formed between the second electrodes, wherein the DC voltage is applied between the first electrode and the second electrode to form an electric field, the electric field is directed from the first electrode to the substrate and directly to the second electrode, And the uncharged aerosol droplets passing downward through the perforation in the first electrode, passing through the electric field, and then toward the perforation in the second electrode, while applying the electric field to the aerosol droplets, And then the aerosol droplets flow into a substrate processing area through the perforations in the second electrode; a substrate pedestal, the substrate pedestal is set on the substrate in the chamber In the processing area, the substrate base is configured to support the substrate during the processing of the film. The substrate processing chamber according to claim 1, wherein the DC voltage is selected to form an electric field having an amplitude between 500 V/cm and 20000 V/cm. The substrate processing chamber according to claim 1, wherein an amplitude of a DC voltage difference is between 100V and 2KV. The substrate processing chamber according to claim 1, wherein the first electrode and the second electrode are horizontal. The substrate processing chamber according to claim 1, wherein the substrate is parallel to both the first electrode and the second electrode. The substrate processing chamber according to claim 1, wherein the substrate is disposed between the first electrode and the second electrode. The substrate processing chamber according to claim 1, further comprising a piezoelectric transducer, and the piezoelectric transducer is in direct contact with the condensed substance precursor. The substrate processing chamber according to claim 1, wherein the condensed substance precursor is a liquid precursor. The substrate processing chamber according to claim 1, wherein the condensed substance precursor is formed by dissolving a solid precursor in a solvent. The substrate processing chamber according to claim 1, wherein the The substrate is perpendicular to both the first electrode and the second electrode. A method of processing a layer on a substrate, the method comprising the following steps: placing the substrate in a substrate processing area of a substrate processing chamber; dissolving a solid precursor in a solvent for an aerosol generation A precursor solution is formed in the vessel; a carrier gas flows into the aerosol generator to generate aerosol droplets; the aerosol droplets pass downward through a perforation in a top electrode, and pass through the aerosol An electric field under the top electrode, and then towards the perforation in a bottom electrode, where the aerosol droplets are not charged; the electric field is applied to the top electrode and the bottom electrode by applying a voltage between the top electrode and the bottom electrode Aerosol droplets; allowing the aerosol droplets to flow into the substrate processing area through the perforations in the bottom electrode; and etching the layer on the substrate by chemical reaction with the aerosol droplets. The method according to claim 11, wherein the layer is composed of two elements. The method according to claim 11, further comprising the following steps: flowing a second precursor into the substrate processing area for Remove a single layer from this layer. The method according to claim 11, wherein the electric field is a DC electric field having an electric field directed to the substrate. The method according to claim 11, wherein the electric field has an amplitude between 500 V/cm and 20000 V/cm. A method of forming a layer on a substrate, the method comprising the following steps: putting the substrate into a substrate processing area of a substrate processing chamber; putting a liquid precursor into an aerosol generator; making a carrier gas Flow into the aerosol generator to generate aerosol droplets; make the aerosol droplets pass downward through a perforation in a top electrode, through an electric field under the top electrode, and then toward a bottom The perforation in the electrode, in which the aerosol droplets are not charged; the electric field is applied to the aerosol droplets by applying a voltage between the top electrode and the bottom electrode; the aerosol droplets are made Flow into the substrate processing area through the through holes in the bottom electrode; and form the layer from the aerosol droplets on the substrate. The method according to claim 16, wherein the layer is a self-assembled single layer (SAM). According to the method described in claim 17, the self-organized single-layer selection Is formed on the exposed copper portion of the substrate instead of on the exposed dielectric portion of the substrate, and the method further includes the following steps: on the exposed dielectric portion without being affected by the self A selectively deposited dielectric is formed on the exposed copper portions blocked by a single layer.

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