TW201637073A - Method of doping semiconductor substrate and method of depositing film containing boron and carbon - Google Patents

Abstract

The present invention provides a method of depositing a film containing boron and carbon. In certain embodiments, a method of depositing a BC film having desirable properties such as conformality and etch rate is provided. One or more boron and/or carbon containing precursors may be decomposed on the substrate at a temperature of less than about 400 °C. One or more of the boron and carbon containing films can have a thickness of less than about 30 angstroms. A method of doping a semiconductor substrate is provided. The doped semiconductor substrate may include: depositing a boron and a carbon film on the semiconductor substrate by exposing the substrate to a vapor phase boron precursor at a process temperature of about 300 ° C to about 450 ° C, wherein the boron precursor comprises boron, carbon, And hydrogen; and annealing the boron and carbon film at a temperature of from about 800 ° C to about 1200 ° C.

Description

Boron deposition and carbonaceous materials

The present invention is generally related to the field of semiconductor device fabrication and, more specifically, to the deposition of materials containing boron and carbon.

Materials containing boron and carbon, such as boron and carbon films, can have a variety of uses, including in the semiconductor industry. The tantalum nitride-based material can be modified to include boron and a carbon component, for example, a tantalum nitride film comprising boron and a carbon component. Boron and carbon films and tantalum nitride films containing boron and carbon components can have various applications in the fabrication process of semiconductor devices.

As the physical geometry of semiconductor devices shrinks, it is desirable to deposit a film on a three-dimensional structure having a high aspect ratio. Accordingly, it is desirable to have a deposition process that provides a film that exhibits conformal coverage of a three-dimensional structure having a high aspect ratio. In addition, it is desirable to have a film that exhibits advantageous etch selectivity to one or more other materials in a semiconductor device and/or a desired etch rate in a dry etch and/or wet etch process.

In some aspects, a method of forming a tantalum nitride film comprising boron and carbon is provided. In some embodiments, a method of depositing a tantalum nitride film comprising boron and carbon on a substrate in a reaction space can include contacting the substrate with a gas phase ruthenium reactant to form a layer on a surface of the substrate a reactant; contacting a surface of the substrate comprising a ruthenium reactant with a nitrogen reactant; and contacting the substrate with a gaseous boron and/or carbon reactant. In some embodiments, contacting the substrate with a gas phase ruthenium reactant, contacting the ruthenium reactant with a nitrogen precursor, and contacting the substrate with at least one of the gas phase boron reactants is performed two or more times. Times.

A method of depositing a tantalum nitride film comprising boron and carbon on a substrate in a reaction space may include: exposing the substrate to a gas phase ruthenium precursor; for example, moving from the reaction space using a purge gas and/or a vacuum Except for excess ruthenium precursor and reaction by-products; contacting the remaining ruthenium reactant on the surface of the substrate with the nitrogen precursor; and exposing the substrate to a vapor phase boron precursor. In some embodiments, exposing the substrate to a gas phase ruthenium precursor, exposing the substrate to a purge gas and/or vacuum, contacting the adsorbed ruthenium reactant with a nitrogen precursor, and At least one of the substrate exposure to the vapor phase boron precursor is performed two or more times.

In some aspects, a method of forming a boron carbon film is provided. In certain embodiments, a method of depositing boron and a carbon film on a substrate in a reaction space can include contacting the substrate with a vapor phase boron precursor at a process temperature of about 325 ° C to about 400 ° C to A boron and carbon film is formed on the substrate, wherein the vapor phase boron precursor is decomposed on the substrate.

In some embodiments, a method of forming a boron and a carbon film on a substrate in a reaction space can include contacting a three-dimensional structure on the substrate with a vapor phase boron precursor at a process temperature of less than about 400 ° C. Boron and carbon films are formed on the three-dimensional structure, wherein the boron and carbon films have a step coverage of greater than about 80%. In certain embodiments, the method can include purging the reaction space after contacting the three-dimensional structure on the substrate with a vapor phase boron precursor.

In some aspects, the method of doping a semiconductor substrate can include: exposing the substrate to a vapor phase boron precursor at a process temperature of about 300 ° C to about 450 ° C. A boron and carbon film is deposited on the substrate, wherein the boron precursor may comprise boron, carbon, and hydrogen. The boron and carbon films can be annealed at a temperature of from about 800 °C to about 1200 °C.

In some aspects, the method of doping a substrate can include depositing a boron and a carbon film on a substrate in the reaction space using a chemical vapor deposition process. The boron and carbon films can be annealed, for example, in a nitrogen atmosphere. In some embodiments, no capping layer is formed on the boron and carbon films prior to annealing. In some embodiments, depositing the boron and carbon film can include exposing a substrate comprising a three-dimensional structure to a vapor phase boron precursor in an inert gas environment at a process temperature greater than about 300 ° C; After the three-dimensional structure on the substrate is exposed to the vapor phase boron precursor, the reaction space is purged.

In some aspects, a method of depositing a film of boron and carbon on a substrate in a reaction space can include contacting the substrate with a vapor phase boron precursor at a process temperature of from about 250 ° C to about 400 ° C. The boron and carbon-containing film is formed on the substrate. In certain embodiments, the vapor phase boron precursor decomposes on the substrate. In certain embodiments, the boron and carbon films have a thickness of less than about 30 angstroms.

In order to summarize the present invention and the advantages achieved over the prior art, certain objects and advantages are set forth herein. Of course, it should be understood that not all such objectives or advantages are necessarily achieved in accordance with any particular embodiment. Thus, it will be appreciated by those skilled in the art that the invention may be practiced or carried out in a manner that can

All such embodiments are intended to be within the scope of the invention as disclosed herein. These and other embodiments will be readily apparent to those skilled in the <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt;

Although certain embodiments and examples are set forth below, it is to be understood by those skilled in the art that the present invention extends beyond the specific disclosed embodiments and/or uses and the obvious modifications and equivalents of the embodiments. Therefore, the scope of the invention disclosed herein is not intended to be limited by the specific embodiments described below.

Films comprising boron and carbon can have a variety of desirable properties including chemical stability, mechanical strength, and thermal and electrical properties. Therefore, such films have a variety of applications in a variety of technical fields, including applications in the semiconductor industry, the medical industry, the military industry, the aerospace industry, and the nuclear industry. For example, a boron carbon film is used as a neutron detector in the fabrication of semiconductor devices and in the fabrication of microelectromechanical systems (MEMS). The boron carbon film can be used for tribological coating of MEMS components and/or as a sacrificial film in a semiconductor device fabrication process. In certain embodiments, the boron and carbon containing film can be used as a capping layer, an etch stop layer, a layer that facilitates photolithographic patterning, and/or a doped layer (eg, as a boron dopant source) ). Other uses besides the semiconductor field will be apparent to those skilled in the art.

In certain embodiments, films consisting essentially of boron and carbon (eg, ultra-thin boron and carbon films) and methods of making such materials are provided. For example, in certain embodiments, boron and carbon films having a thickness in the sub-nanometer range are provided.

In other embodiments, films comprising boron and/or carbon and other components and methods of making such films are disclosed. For example, in certain embodiments, a tantalum nitride film comprising boron and a carbon component can be formed. The tantalum nitride film containing boron and carbon may have various applications including applications in semiconductor devices and the like. The tantalum nitride film comprising boron and carbon components can form part of a semiconductor device (eg, a Fin field-effect transistor (FinFET)) and/or can be part of a process for fabricating a semiconductor device. For example, a tantalum nitride film comprising boron and a carbon component can be deposited on a three-dimensional (3-D) feature during a semiconductor device fabrication process, such as a spacer material that is a gate feature of a transistor (eg, As a spacer material of a gate feature in a multi-gate transistor such as a fin field effect transistor, and/or as a sacrificial layer in a semiconductor device fabrication process.

As described herein, in certain embodiments, boron and carbon (BC) films can be used as dopant films in semiconductor device fabrication processes. For example, boron and carbon films can provide a dopant source for a semiconductor substrate such as a germanium substrate. In certain embodiments, a film consisting essentially of boron and carbon can be used as a solid state diffusion (SSD) layer, wherein boron can be used as a dopant. For example, boron and carbon films can be deposited on the substrate, and the deposited boron and carbon films can then be subjected to an annealing process to drive boron from the boron and carbon films into the underlying substrate.

A capping layer is typically used in conventional solid state doping schemes to reduce or prevent outward diffusion of dopants before, during, or during the annealing process. However, in certain embodiments, boron and carbon solid diffusion layers can be advantageously used as dopant films without the presence or substantial absence of a cap layer directly on the boron and carbon solid diffusion layers. The cover layer used in conventional solid state doping schemes may comprise oxides and/or nitrides. For example, a conventional cover layer may comprise oxides of Group 13, Group 14, or Group 15 elements (including yttrium oxide (eg, SiO ₂ )) and tantalum nitride.

In certain embodiments, a film consisting essentially of boron and carbon can be used as a cover layer formed on a solid diffusion layer. For example, a conventionally formed solid diffusion layer (including a conventionally formed boron-containing solid diffusion layer) may be deposited on a germanium substrate, and a boron and carbon coating layer may be deposited on a conventionally formed solid diffusion layer to The film stack is then subjected to a thermal annealing process to drive the dopant into the underlying germanium substrate. In certain embodiments, the boron and carbon cap layers used in conjunction with the conventionally formed solid state diffusion layer can advantageously provide the desired dopant concentration within the underlying substrate.

One or more processes described herein can be used to form a boron carbon film and/or a tantalum nitride film comprising boron and carbon, wherein the film has one or more desired characteristics, such as conformal coverage of three dimensional features. The desired degree, the desired dry etch rate, the desired wet etch rate, and/or the desired etch selectivity to another material. In certain embodiments, a boron carbon film formed according to one or more processes described herein and/or a tantalum nitride film comprising boron and carbon may exhibit a desired etch selectivity with respect to yttrium oxide. Unless otherwise indicated, the cerium oxide described herein can have any of a plurality of stoichiometric ratios of cerium to oxygen, as will be understood by those skilled in the art to be typical for cerium oxide. In certain embodiments, cerium oxide can include, but is not limited to, cerium oxide (SiO ₂ ). Cerium oxide can be formed according to any of various suitable methods as will be understood by those skilled in the art, and can include, for example, thermal silicon oxide (TOX) (e.g., TOX layer in a semiconductor device), chemistry. Cerium oxide, and/or natural cerium oxide. For example, films deposited according to one or more processes described herein (eg, boron and carbon films or tantalum nitride films containing boron and carbon) can exhibit improved step coverage in wet etchants. a reduced etch rate (eg, a wet etchant that is resistant to, for example, a diluted hydrofluoric acid (HF or dHF) solution (eg, 0.5 wt% HF solution)), and/or a reduced wetness to yttrium oxide Etching rate. For example, one or more of the boron carbon films described herein and/or the tantalum nitride film comprising boron and carbon may exhibit reduced thermal yttrium oxide relative to similar films deposited by other methods. The wet etch rate of TOX) (eg, such that the ratio of the wet etch rate of the tantalum nitride film to the wet etch rate of TOX is less than about 1, including less than about 0.5).

In certain embodiments, the boron and carbon films described herein can be used with another material for enhancing the etch selectivity of the resulting structure formed from boron and carbon films and the other material. For example, in certain embodiments, the boron and carbon films described herein can be used as an etch stop layer under another layer, or as a cover layer over another layer, where boron and carbon films are compared Other layers are more resistant to certain wet etchants (eg, diluted HF solutions).

In certain embodiments, a tantalum nitride film comprising boron and a carbon component can have a desired dielectric constant (kappa-value), such as a spacer material suitable for use as a gate feature of a transistor. In certain embodiments, a tantalum nitride film comprising boron and a carbon component can have a dielectric constant of less than about 7, including between about 4.8 and about 7, and between about 4.8 and about 6. , as described below.

Boron and carbon film

As described herein, a film that is primarily composed of boron and carbon and that is formed according to one or more processes described herein (also referred to below as a boron carbon film or BC film) may advantageously exhibit various Desired characteristics. In certain embodiments, boron and carbon films may advantageously exhibit desired conformality when deposited on a three-dimensional (3-D) feature of the substrate (eg, a 3-D feature having a high aspect ratio). Level. For example, boron and carbon films are deposited to have a thickness of about 3:1 or greater than 3:1 (including about 10:1 or higher than 10:1, about 20:1, or higher than 20:1, about 25:1 Or when the aspect ratio is higher than 25:1, about 40:1 or higher than 40:1, about 50:1 or higher than 50:1, or about 80:1 or higher than 80:1, It may have a conformality of greater than about 90%, including greater than about 95%. In certain embodiments, the boron and carbon films are deposited at an aspect ratio having a ratio of about 20:1 or greater than 20:1 (including about 40:1 or greater than 40:1 and about 80:1 or greater than 80:1). Characteristically, it has a conformality greater than about 90%, including greater than about 95%.

In certain embodiments, the boron and carbon films can exhibit a reduced wet etch rate relative to thermal yttrium oxide. For example, boron and carbon films can exhibit a reduced wet etch rate in a dilute hydrofluoric acid solution (dHF) (eg, an etch rate that is less than about 0.3 times the etch rate of the TOX film exposed to dHF). ). In certain embodiments, the boron and carbon films can have negligible wet etch rates in the diluted HF. In certain embodiments, the boron and carbon films have less than about 0.2 nanometers per minute (nm/min), preferably less than about 0.1 nanometers per minute, and more preferably less than about 0.05 nanometers in diluted HF. /minute wet etch rate. In certain embodiments, the boron and carbon films may comprise nitric acid (HNO ₃ ), sodium hydroxide (NaOH), hydrochloric acid (HCI), sulfuric acid (H ₂ SO ₄ ), and/or phosphoric acid (H ₃ PO ₄ ). The wet etchant exhibits an etch rate of less than about 0.2 nanometers per minute, preferably less than about 0.1 nanometers per minute, and more preferably less than about 0.05 nanometers per minute. In some embodiments, the wet etch rate is lower than the detection limit using one of the etchants listed.

In certain embodiments, the boron and carbon films formed according to one or more processes described herein have a desired film density (eg, from about 2.0 grams per cubic centimeter (g/cm ³ ) to about 2.5 grams per cubic centimeter). The film density of centimeters) exhibits the desired etch resistance. For example, the boron and carbon films can have a wet etch rate as described herein while having a film density of from about 2.0 grams per cubic centimeter to about 2.5 grams per cubic centimeter.

In certain embodiments, the boron and carbon films may exhibit one or more of the desired characteristics prior to being subjected to a post deposition processing process, such as a post deposition processing process as set forth in greater detail herein. In certain embodiments, the post deposition processing process further enhances one or more of the desired characteristics.

In certain embodiments, the boron and carbon films deposited on the surface comprising tantalum (eg, deposited on the surface of a tantalum layer such as a tantalum layer, a tantalum nitride layer, a niobate layer, etc.) can be compared, for example, to The deposition of boron and carbon films on surfaces formed from different materials, such as materials that do not contain germanium, exhibits increased uniformity and/or conformality. For example, boron and carbon films deposited on a surface of tantalum nitride (SiN) (eg, deposited on a surface of a tantalum nitride layer, such as deposited on a tantalum nitride substrate) may exhibit increased uniformity. Without being bound by any particular theory or mode of operation, the improved interaction between the surface of the lanthanide and one or more components of the boron and carbon film may advantageously promote uniformity and/or conformality of the deposited film. .

As noted above, boron and carbon films typically comprise primarily boron and carbon. For convenience and simplicity, the chemical formula of boron and carbon membranes is commonly referred to herein as BC. However, those skilled in the art will appreciate that the actual chemical formula of the BC film can be B _x C. In certain embodiments, for example, x can vary from about 0.1 to about 25. In certain instances, x preferably varies from about 1 to about 10, and more preferably from about 1 to about 2. For example, x can be about 1.5.

In certain embodiments, the chemical vapor deposition (CVD) process is at a temperature of less than about 400 ° C and at a temperature of from about 0.001 Torr to about 760 Torr (including from about 1 Torr to about 10 Torr, or about 0.001 Torr). Boron and carbon films are deposited on the substrate under a pressure of about 10 Torr, which includes decomposing one or more boron precursors (e.g., boron reactants) on the surface of the substrate. In certain embodiments, the boron precursor can comprise both boron and carbon. Thus, in certain embodiments, a CVD process for depositing boron and carbon films can include decomposing a single boron precursor comprising both boron and carbon in a deposition process without any additional precursors. In certain embodiments, the CVD process includes decomposing two or more precursors on the surface of the substrate to form boron and carbon films. In certain embodiments, at least one of the two or more precursors comprises boron (B). In certain embodiments, at least one of the two or more precursors comprises carbon (C). In certain embodiments, the two or more precursors can each comprise boron and carbon. For example, a CVD process for depositing boron and carbon films can include decomposing two or more precursors, each of which comprises both boron and carbon. In certain embodiments, the CVD process does not include any additional precursors other than the boron precursor (eg, does not include any precursors for providing boron and carbon in the carbon film, respectively).

In certain embodiments, no plasma is used or substantially absent in the deposition of boron and carbon films (eg, no or substantially no plasma is used for boron and carbon film growth). In certain embodiments, the CVD process can be a pulsed thermal CVD process in which a plurality of pulses of a single boron precursor are provided to deposit a film having a desired thickness. In certain embodiments, a single pulse of the boron precursor is provided to deposit a film having a desired thickness. The thermal CVD process may include no plasma or substantially no plasma in the decomposition of the precursor. In certain embodiments, a purge step can be performed between boron precursor pulses, such as to remove excess reactants and/or reaction byproducts from the reaction space. In some embodiments, the substrate can be moved to a space where the substrate is not exposed to the precursor.

In certain embodiments, the boron precursor pulse may comprise one or more carrier gases, such as nitrogen and/or a noble gas (eg, argon, helium, neon, and/or xenon). In certain embodiments, the boron precursor pulse comprises a mixture of two or more carrier gases. In certain embodiments, the mixture of two or more carrier gases comprises argon and/or hydrogen. For example, the mixture of two or more carrier gases may comprise two or more gases selected from the group consisting of nitrogen, helium, neon, xenon, argon, and hydrogen.

In certain embodiments, the process for depositing boron and carbon films comprises a single carrier gas and a single boron precursor, wherein the single boron precursor comprises both boron and carbon. In certain such embodiments, the process does not include any other precursors or carrier gases. For example, a single carrier gas can include nitrogen (N ₂ ) or an inert gas (such as argon (Ar) gas or helium (He) gas). For example, the boron precursor is pulsed for a single process may comprise a boron precursor and a nitrogen gas (N _2), argon (Ar) gas or helium (He) gas. In certain embodiments, the process for depositing boron and carbon films comprises a carrier gas mixture and a single boron precursor, wherein the single boron precursor comprises both boron and carbon. In certain such embodiments, the process does not contain any other gases than the carrier gas mixture and the single boron precursor. In such embodiments, the carrier mixture can comprise nitrogen (N ₂ ) and an inert gas. For example, the carrier gas mixture can include nitrogen (N ₂ ) and argon (Ar), or nitrogen (N ₂ ) and helium (He). For example, the boron precursor is pulsed for a single process may comprise a boron precursor and a nitrogen (N ₂₎ and argon (Ar) gas or a single boron precursor and a nitrogen (N ₂₎ and helium (He) gas.

As described in more detail below, in certain embodiments, the CVD process is a cyclic deposition process in which reactants are provided cyclically. For example, depositing boron and carbon films on a substrate can include two or more deposition cycles in which the substrate is contacted with a reactant to achieve a desired film thickness. In other embodiments, the CVD process can be a continuous flow process. For example, depositing boron and carbon films on a substrate can include continuously or substantially continuously exposing the substrate to the reactants for a single period of time to achieve a desired film thickness.

FIG. 1 shows a flow diagram 100 illustrating a process for forming a boron and carbon (BC) film. In block 102, the substrate is exposed to one or more vapor phase boron reactants (eg, boron and/or carbon precursors). The one or more gas phase boron reactants can be delivered to the substrate using a carrier gas. In some embodiments, although the carrier gas has no or substantially no growth of boron and carbon film, the carrier gas may promote one or more between the reactants and/or between the reactants and the substrate surface. Interactions are used to form boron and carbon films.

In certain embodiments, the substrate is exposed to a single gas phase boron reactant. In certain embodiments, the single gas phase boron reactant comprises both boron (B) and carbon (C). In certain embodiments, the substrate is exposed to two or more gas phase reactants. For example, at least one of the two or more gas phase reactants comprises carbon (C), and at least one of the two or more gas phase reactants comprises boron (B) .

In certain embodiments, the carrier gas can include an inert carrier gas such as argon (Ar), nitrogen (N ₂ ), helium (He), helium (Xe), and/or helium (Ne). In certain embodiments, the carrier gas can include a mixture of two or more gases including two or more gases selected from the group consisting of nitrogen, helium, neon, xenon, argon, and hydrogen. In block 104, the step of exposing the substrate to the carrier gas and one or more gas phase boron reactants may be repeated a plurality of times, for example, in a pulsed CVD process. For example, the substrate can be exposed to the carrier gas and the one or more fumed boron reactants for a first duration, and the exposing step can be repeated from about 5 times to about 5,000 times, including about 100 times to About 3,000 times (including about 1,000 times, and about 2,000 times). In certain embodiments, the exposing step can be repeated less than about 100 times, including from about 1 to about 100, from about 2 to about 50, from about 3 to about 20, or about 5 Twice to about 10 times.

The duration may be the same in each of a plurality of repetitions or cycles or may vary between one or more cycles. The number of repetitions can be selected, for example, to facilitate deposition of boron and carbon films having the desired thickness. In certain embodiments, the one or more gas phase boron reactant streams may be discontinued into the reaction space after exposing the substrate to a carrier gas and the one or more gas phase boron reactants. In certain embodiments, the step of performing a purge step and/or transporting the substrate to a space remote from the reactants after exposing the substrate to the carrier gas and the one or more vapor phase boron reactants (eg, The substrate is not exposed to or substantially not exposed to the reactants). The purge step can be used to remove one or more excess reactants and/or reaction byproducts from the reactor chamber. In certain embodiments, the purging step and/or the step of transporting the substrate is followed by each time the substrate is exposed to a carrier gas and the one or more fumed boron reactants. For example, after each exposure of the substrate to the reactants in each cycle, the substrate can be moved to a non-reactant or substantially non-reactive space, or the excess reactants in the reactor can be purged and removed. / or reaction by-products. In certain embodiments, the purging step includes continuously flowing a carrier gas (eg, causing a carrier gas (eg, at least one component of the multicomponent carrier gas) to be the same as the flow rate during the reactant pulse or Different flow rates flow continuously). For example, the process 100 for depositing boron and carbon films can include continuously flowing a carrier gas to periodically flow the one or more gas phase boron reactants.

In some embodiments, the process for depositing boron and carbon (BC) films can include a chemical vapor deposition (CVD) process. Referring to Figure 1, in certain embodiments, process 100 includes a thermal CVD process performed at a reduced process temperature (e.g., a temperature of less than about 400 °C). The thermal CVD process can be a process in which no plasma is applied or substantially applied, for example, to facilitate decomposition of the precursor used to deposit the film. Process temperatures as referred to herein may include the reactor chamber susceptor, the temperature of the reactor chamber walls, and/or the temperature of the substrate itself. For example, in certain embodiments, the process 100 for depositing boron and carbon films can be performed at process temperatures up to about 400 °C. In certain embodiments, the process 100 for depositing boron and carbon films can range from about 325 ° C to about 400 ° C, preferably from about 350 ° C to about 400 ° C, and optimally from about 375 ° C to about 400 ° C. Temperature to perform. Without being bound by any particular theory or mode of operation, the deposition of boron and carbon films at temperatures less than about 400 ° C advantageously facilitates deposition in surface reaction limited regimes to facilitate formation. The boron and carbon films of the one or more desired characteristics (eg, increased conformal performance, increased uniformity, and/or reduced etch rate).

In certain embodiments, the deposition of boron and carbon (BC) films can be performed at a process temperature of from about 200 °C to about 450 °C, including, for example, from about 250 °C to about 400 °C or from about 400 °C to about 425 °C.

In certain embodiments, boron and carbon can be performed, for example, in a single wafer reactor at process temperatures up to about 450 ° C (including from about 300 ° C to about 450 ° C or from about 400 ° C to about 425 ° C). The deposition of the film. For example, in certain embodiments, boron and carbon films can be deposited at a process temperature of from about 400 °C to about 450 °C (eg, at about 430 °C). For example, deposition of boron and carbon films can be performed in a single wafer reactor at process temperatures from about 400 °C to about 425 °C.

In certain embodiments, the deposition of boron and carbon (BC) films can be performed at process temperatures up to about 400 °C. For example, in certain embodiments, the batch can be processed at a process temperature of from about 250 ° C to about 400 ° C, preferably from about 275 ° C to about 375 ° C, and more preferably from about 300 ° C to about 350 ° C. The deposition of boron and carbon (BC) films is performed in the treatment reactor.

According to some embodiments of the invention, the pressure in the reactor chamber during the treatment is maintained from about 0.001 Torr to about 760 Torr, including from about 0.01 Torr to about 50 Torr, preferably from about 0.1 Torr to about 10 Torr, and more preferably. The ground is about 1 Torr to about 10 Torr. In certain embodiments, the deposition of boron and carbon films can be performed at a reactor chamber pressure of from about 0.5 Torr to about 8 Torr. For example, the reactor chamber pressure can be about 6 Torr. The selected chamber pressure can be used to facilitate the formation of the desired boron and carbon films. In certain embodiments, the chamber pressure can be selected based on the configuration of the reactor chamber (eg, a batch reactor or a single wafer reactor). In certain embodiments, the batch processing reactor can have a reactor chamber pressure of from about 0.001 Torr to about 10 Torr. In some embodiments, the chamber pressure can be selected to provide boron and carbon films with desired conformality and/or etch rate performance.

As noted above, the carrier gas can include an inert carrier gas such as nitrogen (N ₂ ), helium (He), helium (Xe), and/or helium (Ne). For example, block 102 of FIG. 1 can include exposing the substrate to one or more boron reactants and nitrogen. Without being limited by any particular theory or mode of operation, nitrogen, helium, neon, and xenon may exhibit increased thermal conductivity (eg, compared to other inert carrier gases such as argon (Ar)). A higher thermal conductivity of the thermal conductivity) whereby the decomposition of the one or more boron and/or carbon precursors is facilitated. Moreover, without any particular theory or mode of operation, a carrier gas having increased thermal conductivity may facilitate decomposition of the one or more boron and/or carbon precursors in the high aspect ratio features of the 3-D substrate surface. To facilitate conformal and/or etch-resistant boron and carbon films on high aspect ratio features. For example, a carrier gas including nitrogen, helium, neon, and/or xenon (including a carrier gas including two or more of nitrogen, helium, neon, xenon, argon, and/or hydrogen) The mixture) can be advantageous for forming conformal and/or etch resistant boron and carbon films.

In certain embodiments, the carrier gas can include argon (Ar). For example, block 102 of FIG. 1 can include exposing the substrate to one or more gas phase boron reactants and argon.

In certain embodiments, the flow of one or more of the gas phase boron reactants into the reaction space can be continuous or substantially continuous. For example, process 100 for depositing boron and carbon (BC) films can include a continuous flow thermal CVD process. For example, the one or more vapor phase boron reactants can be continuously flowed into the reaction chamber until the desired boron and carbon film thickness is achieved. In certain embodiments, the flow rate of boron reactants and/or carrier gases can be varied during a continuous flow thermal CVD process to provide the desired boron and carbon films. In certain embodiments, the process temperature and/or reactor chamber pressure may be varied during a continuous flow thermal CVD process to provide the desired boron and carbon films.

In certain embodiments, the process 100 for depositing boron and carbon (BC) films includes a pulsed thermal CVD process. In certain embodiments, process 100 can include a cyclic deposition process. For example, the cycle of process 100 can include contacting the substrate with the reactants for a desired period of time, for example, by supplying a reactant pulse into the reactor chamber for a desired duration. The reactant pulse can comprise a carrier gas (eg, argon, nitrogen, helium, and/or helium) and at least one or more boron reactants. In certain embodiments, the reactants are pulsed multiple times to deposit boron and carbon films having a desired thickness and/or composition (eg, repeating multiple cycles, each cycle including reactant pulses).

In certain embodiments, the step of not exposing the substrate to the reactants, such as a purge step and/or transporting the substrate to an unreacted or substantially non-reactive, may be performed after one or more reactant pulses. Steps in space. For example, the substrate can first be delivered to a non-reactant or substantially non-reactant space, and then any excess reactants and/or reaction by-products in the reactor chamber can be purged. In certain embodiments, the step of purging and/or transporting the substrate to a space free of reactants or substantially no reactants may be performed after each of the plurality of reactant pulses. The purge step can be used to remove one or more excess reactants and/or reaction byproducts from the reactor chamber. For example, the purging step can include: flowing one or more purge gases through the reactor chamber, and/or (eg, by evacuating the reactor chamber to a vacuum) to evacuate the reactor chamber to remove or substantially Excess reactants and/or reaction by-products are removed. In certain embodiments, the purge gas comprises an inert gas. In certain embodiments, the purge gas comprises nitrogen. In certain embodiments, the purge gas comprises an inert gas. In certain embodiments, the purge gas comprises argon.

In certain embodiments, the step of suspending the one or more gas phase boron reactant streams into the reactor chamber to continuously flow the carrier gas may be performed after the reactant pulse. For example, the purging step can include continuously flowing a carrier gas (eg, at a flow rate that is the same or different than the flow rate during the reactant pulse, such as a higher flow rate) to remove the reaction from the reaction chamber. Things. In certain embodiments, the purging step can include continuously flowing at least one component of the carrier gas comprising the mixture of two or more gases to remove excess reactants from the reactor chamber. In certain embodiments, the process 100 for depositing boron and carbon films can include continuously flowing a carrier gas and alternately flowing the one or more gas phase boron reactants.

The duration of the reactant pulse can be selected to provide the desired amount of one or more boron reactants and/or the desired amount of deposition to the reactor chamber. In certain embodiments, the reactant pulse can have a duration of from about 0.1 second to about 5 seconds, including from about 0.1 second to about 1 second. For example, the reactant pulse can have a duration of about 0.5 seconds. In certain embodiments, the reactant pulse can have a duration of about 0.3 seconds.

In certain embodiments, the spacing between reactant pulses can range from about 1 second to about 15 seconds. In certain embodiments, the spacing includes a purge step that removes excess reactants and/or reaction byproducts from the reactor chamber. In certain embodiments, the spacing includes the step of transporting the substrate to a space that is unreacted or substantially non-reactive. For example, the spacing can include the step of transporting the substrate to a non-reactive or substantially non-reactive space, and having a duration of from about 0.5 seconds to about 15 seconds, including from about 1 second to about 10 seconds. Purging step. For example, the purge step can have a duration of about 5 seconds. In certain embodiments, the purging step can have a duration of about 1 second.

In certain embodiments, the duration of the reactant pulses and/or the spacing between reactant pulses (eg, including, for example, the duration of the purge step) can be selected based on the substrate on which the boron and carbon films are deposited. The surface area, the aspect ratio of the three-dimensional (3-D) structure on which the boron and carbon films are deposited, and/or the configuration of the reactor chamber. For example, the spacing between reactant pulses and/or reactant pulses can have an increased duration for depositing boron and carbon films on a larger surface area, a 3-D structure having an increased aspect ratio, And/or deposition in a batch reactor. In certain embodiments, the increased reactant pulse duration and/or the spacing between reactant pulses is selected to be in the ultra-high aspect ratio feature (including, for example, having about 40:1 and greater than 40:1 (including about 80:1) And deposition on a feature of an aspect ratio greater than 80:1).

In certain embodiments, the one or more boron reactants are supplied to a reactor chamber from a respective source vessel in which the reactants are stored as a vapor. The vapor pressure of each reactant can facilitate delivery of the reactants into the reactor chamber. For example, vaporization techniques can be utilized to provide gasification reactants to the reactor chamber. In certain embodiments, the source container can be maintained at a temperature of from about 20 °C to about 25 °C. The mass flow rate of the gasification reactant stream to the reactor chamber can be controlled, for example, by controlling the extent to which the supply valve for providing the gasification reactants to the reactor chamber remains open.

In certain embodiments, a suitable boron reactant can comprise one or more compounds containing a BC bond. In certain embodiments, a suitable boron reactant can comprise a boron compound having at least one organic ligand. In certain embodiments, the organic ligand can have a double bond and/or a triple bond. In certain embodiments, the organic ligand can be a ring ligand. In certain embodiments, the organic ligand may comprise a delocalized electron. In certain embodiments, a suitable boron reactant can comprise a trialkyl boron compound. In certain embodiments, a suitable boron reactant can comprise triethylboron (B(C ₂ H ₅ ) ₃ , triethylboron, TEB). In certain embodiments, a suitable reactant may comprise boron trimethyl boron _{(B (CH 3) 3,} trimethylboron, TMB). In certain embodiments, a suitable boron reactant can comprise three having a linear or branched alkyl group (including, for example, a linear or branched C3-C8, and more preferably a linear or branched C3-C5). Alkyl boron compound. Suitable boron reactants can include a variety of other boron-containing reactants. In certain embodiments, the boron reactant can comprise a boron halide, an alkyl boron, and/or a borane. In certain embodiments, the boron reactant can comprise a boron halide, a borane halide, and a complex thereof. For example, a suitable boron halide can have a boron to halide ratio of from about 0.5 to about 1.

Suitable boranes may comprise a compound according to formula I or formula II.

B _n H _n+x (Formula I)

Wherein n is an integer from 1 to 10, preferably from 2 to 6, and x is an even number, preferably 4, 6 or 8.

B _n H _m (Formula II)

Wherein n is an integer from 1 to 10, preferably from 2 to 6, and m is an integer from 1 to 10, preferably from 2 to 6, different from n.

Examples of the above-described borane according to the chemical formula I include nido-borane (B _n H _n+4 ), arachno-borane (B _n H _n+6 ), and open-net type ( Hyph)-borane (B _n H _n+8 ). Examples of the borane according to Chemical Formula II include a condensed (conjuncto)-borane (B _n H _m ). Further, a borane complex such as (CH ₃ CH ₂ ) ₃ N--BH ₃ can be used.

In certain embodiments, suitable boron reactants can include borane halides, particularly fluorides, bromides, and chlorides. An example of a suitable compound is B ₂ H ₅ Br. Other examples include boron halides having a high boron / halide ratio, such as _{B 2 F 4, B 2 C} l4 and B ₂ Br _4. Halogenated borane complexes can also be used.

In certain embodiments, a halogenoborane according to Formula III can be a suitable boron reactant.

B _n X _n (chemical formula III)

Wherein X is chlorine (Cl) or bromine (Br), and when X is chlorine, n is an integer of 4 or 8 to 12, or n is an integer of 7 to 10 when X is bromine.

In certain embodiments, the carborane according to Formula IV can be a suitable boron reactant.

C ₂ B _n H _n+x (Formula IV)

Examples of carboranes according to Formula IV include closo-carbobane (C ₂ B _n H _n+2 ), nested-carbobane (C ₂ B _n H _n+4 ), and cobwebs Carborane (C ₂ B _n H _n+6 ).

In certain embodiments, the amine-borane adduct according to Formula V can be a suitable boron reactant.

R ₃ NBX ₃ (chemical formula V)

Wherein R is a straight or branched chain C1 to C10, preferably a C1 to C4 alkyl group or H, and X is a linear or branched C1 to C10 group, preferably a C1 to C4 alkyl group, H or a halogen.

In certain embodiments, the amine borane according to Formula VI, wherein one or more of the substituents on the boron are amine groups, can be a suitable boron reactant.

R ₂ N (chemical formula VI)

Wherein R is a linear or branched C1 to C10, preferably a C1 to C4 alkyl group or a substituted or unsubstituted aryl group.

An example of a suitable amine borane is (CH ₃ ) ₂ NB(CH ₃ ) ₂ .

In certain embodiments, a suitable boron reactant can comprise a cyclazepine (--BH--NH--) ₃ and/or a volatile derivative thereof.

In certain embodiments, the alkyl boron or alkyl borane can be a suitable boron reactant wherein the alkyl group is typically a linear or branched C1 to C10 alkyl group, preferably a C2 to C4 alkyl group.

According to certain embodiments, the process for depositing boron and carbon (BC) films includes a pulsed thermal CVD process performed at a process temperature of from about 375 ° C to about 400 ° C and at a pressure of from about 0.5 Torr to about 3 Torr. . The process can include contacting the substrate with a reactant pulse comprising nitrogen as a carrier gas and comprising triethylboron (TEB) as the boron and carbon reactant. The supply of TEB can be extracted from a source vessel for storing TEB at a temperature of from about 20 ° C to about 25 ° C (eg, a needle valve for flowing TEB into the reactor chamber can be rotated about two turns to remain open). The reactant pulse can have a duration of about 0.5 seconds. In certain embodiments, a single cycle of the process can include following the reactant pulse followed by a period of time in which the substrate is not exposed to the reactants, such as a purge step. The purging step can include flowing nitrogen gas rather than reactants, for example for a duration of about 5 seconds. The process can include repeating the cycle of performing the purge step after the reactant pulse to multiple times to achieve a boron and carbon film having a desired thickness and/or composition. For example, the cycle can be repeated about 1,000 times, about 1,500 times, about 2,000 times, or about 5,000. In certain embodiments, the cycle can be repeated from about 2 times to about 1,000 times, including from about 2 times to about 2,000 times, from about 3 times to about 2,000 times, or from about 5 times to about 5,000 times. In certain embodiments, the cycle can be repeated from about 50 times to about 2,000 times. In certain embodiments, the cycle can be repeated from about 100 times to about 1,500 times. In certain embodiments, the cycle can be repeated up to about 100 times. In certain embodiments, the cycle can be repeated from about 1 to about 100, from about 10 to about 100. In certain embodiments, the cycle can be repeated from about 2 times to about 50 times, from about 3 times to about 20 times, or from about 5 times to about 10 times.

One or more boron and carbon (BC) films formed in accordance with one or more processes described herein may advantageously exhibit the desired conformality when deposited on a high aspect ratio feature of the 3-D substrate surface, And/or desired etch rate performance (eg, wet etch rate performance, such as wet etch rate performance in diluted HF solution). The membrane also exhibits a reduced density of the film, for example about 2.0 g / cc (g / cm ³⁾ to about 2.5 g / cc density film. In certain embodiments, such as when boron and carbon films are formed to have a ratio of about 3:1 or greater than 3:1 (including about 10:1 or greater than 10:1, about 25:1, or greater than 25:1). Boron and carbon films may exhibit greater than about 80%, preferably greater than about 90%, and more preferably greater than about 95, or a 3-D structure having an aspect ratio of about 50:1 or greater than 50:1). % conformality. In certain embodiments, when boron and carbon films are formed with an aspect ratio of about 20:1 or greater than 20:1, about 40:1, or greater than 40:1, or about 80:1 or greater than 80:1 The boron and carbon films may exhibit a conformality of greater than about 80%, preferably greater than about 90%, and more preferably greater than about 95%, on the 3-D structure. For example, one or more boron and carbon films formed in accordance with one or more processes described herein when deposited on a 3-D substrate surface have a high aspect ratio (including up to about 250:1 (including about 150:1 and An aspect ratio of about 100:1) can characteristically exhibit a conformal performance of greater than about 95%.

As described herein, in certain embodiments, boron and carbon (BC) films can be used as sacrificial films in semiconductor device fabrication processes. For example, boron and carbon films can be selectively removed during the etching process. In some embodiments, boron and carbon films can form part of a fabricated semiconductor device. For example, boron and carbon films can be more resistant to etching than one or more other materials used in the fabrication of semiconductor devices. In some embodiments, the boron and carbon films can be etched by a dry etch process and/or a wet etch process. In some embodiments, an etching process including chlorine (Cl) and/or fluorine (F) (eg, a plasma process containing chlorine and/or fluorine) may be utilized to selectively remove sacrificial during fabrication of the semiconductor device. Boron and carbon film. In certain embodiments, the boron and carbon films may be more resistant to one or more etchants, including wet etchants such as diluted HF solutions.

In certain embodiments, the boron and carbon films can exhibit the desired wet etch selectivity, such as wet etch selectivity to a thermal yttrium oxide (TOX) layer. For example, boron and carbon films can be more resistant to wet etching than hot ruthenium oxide layers such that the ratio of wet etch rate of boron and carbon film to wet etch rate of the thermal yttrium oxide layer is less than about 1 (eg, at In the diluted HF solution), less than about 0.5, or less than about 0.3. In certain embodiments, the ratio of the wet etch rate of the boron and carbon films to the wet etch rate of the thermal yttrium oxide layer can be less than about 0.1. In certain embodiments, the ratio of the wet etch rate of the boron and carbon films to the wet etch rate of the thermal yttrium oxide layer can be less than about 0.05.

In certain embodiments, the boron and carbon films can advantageously exhibit a desired wet etch rate, including an etch rate in a dilute HF solution. For example, the boron and carbon films can advantageously exhibit less than about 0.2 nanometers per minute (nm/min) (including preferably less than about 0.1 nanometers per minute, more preferably less than about 0.05 nanometers per minute, and An etch rate that is optimally less than about 0.02 nm/min. As will be explained in more detail below, ultra-thin boron and carbon materials deposited according to one or more of the processes described herein can advantageously exhibit the desired resistance to wet etchants such as diluted HF. In certain embodiments, the ultra-thin boron and carbon films are tolerant or substantially resistant to diluted HF for greater than about 30 seconds, preferably greater than about 60 seconds, or more preferably greater than about 120 seconds. In certain embodiments, ultra-thin boron and carbon films can tolerate or substantially tolerate diluted HF exposure for up to about 5 minutes, or up to about 10 minutes. For example, ultra-thin boron and carbon films can exhibit less than about 0.1 nanometers per minute, less than about 0.05 nanometers per minute, or less than about 0.02 nanometers per minute when exposed to diluted HF for at least the indicated number of times. Etching rate. In certain embodiments, ultra-thin boron and carbon films can tolerate or substantially tolerate diluted HF exposure for longer than 10 minutes.

In certain embodiments, the boron and carbon films can exhibit less than about 0.2 nanometers per minute (including preferably less than about 0.1 nanometers per minute, and more preferably less than about 0.1 nanometers per minute, more preferably in the following wet etchant solutions and at specified temperatures Wet etch rate of less than about 0.05 nanometers per minute, and optimally less than about 0.02 nanometers per minute: phosphoric acid at a concentration of about 85% by weight at about room temperature (eg, a temperature of about 25 ° C) H ₃ PO ₄₎ was concentrated at about 80 ℃ HNO ₃ nitric acid solutions (e.g., having about 65 wt% to about 75% by weight concentration solution of HNO _3), at about room temperature (e.g., about 25 deg.] C of At a temperature of 5.5% by weight of hydrofluoric acid (HF), at a temperature of about room temperature (for example, a temperature of about 25 ° C), the ratio of nitric acid: hydrofluoric acid: water (HNO ₃ : HF: H ₂ O) is about 1 : a solution of 1:5, having an aqueous solution of sodium hydroxide (NaOH) having a concentration of about 10% by weight at about room temperature (for example, a temperature of about 25 ° C), at about room temperature (for example, a temperature of about 25 ° C) a concentrated hydrochloric acid (HCl) solution (eg, a solution having a HCl concentration of from about 35% to about 40% by weight), and at about room temperature (eg, about 25) Concentrated sulfuric acid solution at a temperature) (H ₂ SO ₄₎ (e.g., greater than about 90 wt% H ₂ SO ₄ concentration of the solution).

In certain embodiments, the boron and carbon films can be selectively removed. In certain embodiments, the boron and carbon films can have an etch selectivity of about 5 or greater than about 5 or greater than 5 for another material in the device (eg, a film having a different composition), including about 10 or greater than 10, about 20, or Selectivity greater than 20, or about 50 or greater than 50.

In some embodiments, for example, a portion of the boron and carbon film deposited on the sidewalls of the three-dimensional structure may exhibit a desired etch rate as compared to the etch rate of a portion of the film deposited on the top surface of the three-dimensional feature. In some embodiments, a portion of the boron and carbon film deposited on the sidewalls of the three-dimensional structure can exhibit a uniform or substantially uniform etch as a portion of the boron and carbon film deposited on the top surface of the structure. rate. For example, the ratio of the etch rate of the sidewall portions of the boron and carbon films to the etch rate of the top portions of the boron and carbon films can be less than about 4, including less than about 2, about 1.5. In certain embodiments, the ratio is about 1. In certain embodiments, the boron and carbon films maintain uniformity of the top and sidewall portions of the boron and carbon films after exposure to one or more plasma processes, such as the post-plasma deposition process described herein. degree.

One or more process parameters for the boron and carbon (BC) film growth process can be adjusted to achieve the desired boron and carbon film characteristics. For example, the boron reactant, the duration of the reactant pulse, the duration of the purge step, the process temperature, and/or the number of repetitions of the reactant pulse can be determined to provide boron and carbon films containing the desired characteristics. . In certain embodiments, one or more parameters of one cycle of the reactant pulse and purge step may be different from another cycle (eg, one cycle of the reactant pulse and purge step as described with reference to FIG. 1) One or more parameters. In certain embodiments, the boron reactant can have a B-C bond. In certain embodiments, the boron reactant comprises at least one organic ligand, such as a hydrocarbon ligand, including a boron reactant comprising an alkyl group.

As described herein, ultra-thin boron and carbon films can be formed on a substrate using one or more of the processes described herein, wherein the boron and carbon films have a thickness in the nanometer range. In certain embodiments, the ultra-thin boron and carbon films can have a thickness of less than about 30 angstroms (Å), less than about 20 angstroms, less than about 15 angstroms, less than about 10 angstroms, or less than about 7 angstroms. In certain embodiments, the ultra-thin boron and carbon films can have a thickness of less than about 5 angstroms. In certain embodiments, the ultra-thin boron and carbon films can have a thickness of less than about 3 angstroms (eg, about 1 angstrom).

In some embodiments, ultra-thin boron and carbon films, although referred to herein as films, may not form a continuous layer on the substrate. For example, ultra-thin boron and carbon films may not completely cover all surfaces of the substrate material on which the ultra-thin boron and carbon films are formed. In certain embodiments, the ultra-thin boron and carbon films can comprise pinholes. The thickness of the ultra-thin boron and carbon films described herein refers to the average thickness of the film. In certain embodiments, the ultra-thin boron and carbon films can form a continuous layer on the substrate.

In certain embodiments, ultra-thin boron and carbon films can be formed in accordance with one or more cycling processes described herein, such as the cyclic pulse CVD process described herein. In some embodiments, ultra-thin boron and carbon films can be deposited by a pulsed thermal CVD process. For example, a cycle of a pulsed CVD process for forming ultra-thin boron and carbon films can include exposing the substrate to one or more boron precursors for a certain duration, followed by (eg, by removing the substrate to The substrate without precursor or substantially no precursor, and/or by performing a purge step) does not expose the substrate to the spacing of the boron precursor. The one or more boron precursors may be supplied to the reaction space with the attendant of a carrier gas as described herein. In certain embodiments, the ultra-thin boron and carbon films can be performed by from about 1 to about 100 cycles, preferably from about 2 to about 50 cycles, and more preferably from about 3 to about 20 cycles. To form. In certain embodiments, ultra-thin boron and carbon films can be formed using from about 5 to about 10 cycles.

In certain embodiments, the deposition rate of each cycle of ultra-thin boron and carbon films may depend on the composition of the material on which the ultra-thin boron and carbon materials are deposited. For example, deposition rates on ultra-thin boron and carbon film aluminum nitride (AlN) substrates can be lower than similar or identical ultra-thin boron and carbon film deposition processes on a tantalum nitride (SiN) substrate for deposition. The deposition rate.

In certain embodiments, the process for forming ultra-thin boron and carbon films can include flowing one or more boron precursors continuously or substantially continuously during the deposition process. For example, the process can include a continuous flow thermal CVD process. In certain embodiments, a continuous flow process can provide a process that is shorter than a process that includes multiple pulses of reactants (eg, due to the removal of the purge step). In certain embodiments, a continuous flow process can provide improved uniformity relative to a pulsed process. In certain embodiments, continuous flow may be selected to provide the required accuracy in controlling the precursor dose and/or precursor concentration in the reaction space. In certain embodiments, continuous flow can be selected based on the configuration of the reactor chamber. For example, a continuous flow process can be selected for a reactor chamber having a relatively large reaction space volume. In certain embodiments, a continuous flow process can be selected for the batch reactor. In certain embodiments, a continuous flow process can be selected for a reactor chamber having relatively high precision in dose control. For example, a continuous flow process can be selected for a particular CVD reaction chamber.

In certain embodiments, ultra-thin boron and carbon materials can be formed in a single wafer reactor. In certain embodiments, ultra-thin boron and carbon films can be formed in a batch processing reactor. For example, a deposition process for forming ultra-thin boron and carbon films can be performed in a vertical batch reactor. For example, a batch reactor can be used to process wafer loads of from about 25 wafers to about 200 wafers, preferably from about 50 wafers to about 150 wafers.

As noted above, in certain embodiments, the process temperature for depositing ultra-thin boron and carbon films in a batch reactor can range from about 250 ° C to about 400 ° C, preferably from about 275 ° C to about 375 ° C. And more preferably from about 300 ° C to about 350 ° C.

In certain embodiments, the ultra-thin boron and carbon films can exhibit less than about 5%, preferably less than about 2%, 1 sigma (1 sigma) non-uniformity. For example, ultra-thin boron and carbon films deposited on 300 millimeter (mm) wafers using one or more of the processes described herein can exhibit less than about 2% 1 σ unevenness. In some embodiments, relatively low process temperatures can be used to achieve relatively low uniformity performance.

In some embodiments, ultra-thin boron and carbon films can be used to enhance the etch selectivity of structures comprising ultra-thin boron and carbon films and another different material. For example, the other material can comprise a material that has relatively less resistance to certain etchants, including certain wet etchants, such as diluted HF. The use of ultra-thin boron and carbon films with the other different materials advantageously facilitates the formation of the resulting structure having the desired etch properties and the desired properties of the other different material. For example, ultra-thin boron and carbon films can be used with aluminum nitride and/or aluminum oxide to provide a structure having desired etch characteristics while providing a structure that exhibits desirable electrical and/or optical properties. The structure made.

In certain embodiments, the other material may comprise one or more of a nitride, a carbide, an oxide, and/or a mixture thereof. In certain embodiments, the other material may comprise one or more of a nitride, a carbide, and/or an oxide of a metal and/or a semi-metal. In certain embodiments, the other material may comprise one or more of a metal and/or a semi-metal nitride. For example, the one or more nitrides may comprise tantalum nitride, tantalum nitride, and/or aluminum nitride. In certain embodiments, the other material may comprise one or more of metal and/or semi-metal carbides. In certain embodiments, the other material may comprise one or more of a metal and/or a semi-metal oxide. For example, the one or more oxides can comprise cerium oxide and/or cerium oxide.

In some embodiments, the other material can be formed using an atomic layer deposition (ALD) process and/or a CVD process (including a plasma enhanced ALD process and/or a CVD process). In some embodiments, the other material is preferably formed using an ALD process and, more preferably, a low temperature ALD process (eg, a process temperature of up to about 400 °C). In some embodiments, the other material can be formed in the same tool (eg, a cluster tool) as the ultra-thin boron and carbon materials. For example, a reaction chamber for depositing ultra-thin boron and carbon materials may be located on the same cluster tool as the reaction chamber used to deposit the other material such that the substrate may not be exposed to ambient air. The transfer between the reaction chambers is performed (for example, "in situ"). In some embodiments, the same reaction chamber can be used to deposit ultra-thin boron and carbon materials and both of the other materials, and the substrate is not deposited between depositing ultra-thin boron and carbon material and depositing the other material. Exposure to ambient air.

In some embodiments, the other material may be deposited first and ultra-thin boron and carbon films may be deposited on the other material. For example, the other material may be a substrate on which ultra-thin boron and carbon films are deposited. For example, ultra-thin boron and carbon films can be used as a cover layer for the other material. In some embodiments, ultra-thin boron and carbon films can be deposited first, and the other material deposited on the ultra-thin boron and carbon films. For example, ultra-thin boron and carbon films can be used as an etch stop layer for the other material. The use of ultra-thin boron and carbon films as the capping layer and/or etch stop layer of the other material may facilitate fine tuning of the etch properties of the resulting structure.

In certain embodiments, ultra-thin boron and carbon films having a thickness of less than about 30 angstroms, about 20 angstroms, about 15 angstroms, about 10 angstroms, about 7 angstroms, about 5 angstroms, or about 3 angstroms are tolerable or Removal by dilution of HF is substantially tolerated. An ultra-thin boron and carbon film having such a thickness can be used as an etch stop layer of another material deposited on an ultra-thin boron and carbon film, and/or a cover layer of another material deposited with ultra-thin boron and a carbon film. . In certain embodiments, ultra-thin boron and carbon materials deposited using from about 1 to about 100 deposition cycles, including up to about 50 cycles, about 20 cycles, or about 10 cycles, may exhibit a pair Tolerance or substantial tolerance of etching by diluted HF. Ultra-thin boron and carbon films deposited using less than about 100 deposition cycles can be used as an etch stop layer for another material deposited on ultra-thin boron and carbon films, and/or for deposition of ultra-thin boron and A cover layer of another material of the carbon film.

As noted above, in certain embodiments, boron and carbon (BC) films can be used as dopant films such as solid state diffusion (SSD) layers. In certain embodiments in which boron and carbon films are used as dopant films, no cover layer is required on the boron and carbon films. In some embodiments, the boron and carbon (BC) films themselves can be used as a capping layer on different SSD layers to dope the substrate. The boron and carbon dopant films can be formed according to one or more processes described herein. For example, processes for depositing boron and carbon solid diffusion layers and/or boron and carbon cap layers can include pulsed thermal CVD processes. In certain embodiments, the thermal CVD process can include contacting a surface on which the boron and carbon films are deposited with one or more reactant pulses comprising one or more boron reactants described herein. For example, the reactant pulse can comprise a boron reactant comprising a BC bond, including a boron reactant comprising an organic ligand, such as a trialkyl boron (eg, triethylboron (B(C ₂ H ₅ ) ₃ , TEB), and/or trimethylboron (B(CH ₃ ) ₃ , TMB)). In certain embodiments, the reactant pulse comprises a carrier gas such as argon. For example, a cycle of a thermal CVD process for depositing boron and a carbon solid diffusion layer and/or a boron and carbon cap layer may include a reactant pulse comprising TEB and argon, wherein the reactant is pulsed after the pulse In the step, the purging step includes flowing argon without flowing the TEB stream such that argon gas flows continuously through the cycle while TEB only flows during a portion of the cycle. In certain embodiments, the cycle can be repeated up to about 1,000 times, about 1,500 times, about 2,000 times, or about 5,000. In certain embodiments, the cycle can be repeated from about 2 times to about 1,000 times, including from about 2 times to about 2,000 times, from about 3 times to about 2,000 times, or from about 5 times to about 5,000 times. In certain embodiments, the cycle can be repeated from about 10 times to about 1000 times. In certain embodiments, the cycle can be repeated from about 50 times to about 2,000 times. In certain embodiments, the cycle can be repeated from about 100 times to about 1,500 times.

In certain embodiments, the reactant pulse can have a duration of from about 0.1 second to about 5 seconds, including from about 0.1 second to about 1 second. For example, the reactant pulse can have a duration of about 0.3 seconds. In certain embodiments, the purge step can have a duration of from about 0.5 seconds to about 10 seconds, including from about 0.5 seconds to about 5 seconds. For example, the purge step can have a duration of about 1 second.

In certain embodiments, the process for depositing boron and carbon solid diffusion layers and/or boron and carbon coating layers can range from about 300 ° C to about 450 ° C (including from about 350 ° C to about 450 ° C or from about 400 ° C to about Execution at a process temperature of 450 ° C). For example, boron and carbon solid diffusion layers and/or boron and carbon coatings can be deposited at temperatures of about 430 °C. In certain embodiments, the boron and carbon solid diffusion layers and/or boron and carbon coating layers can be deposited at a reactor chamber pressure of from about 0.5 Torr to about 10 Torr (eg, about 6 Torr).

In some embodiments, the thickness of the boron and carbon films can be selected to provide the desired doping on the underlying substrate. For example, the thickness of the boron and carbon solid diffusion layers and/or boron and carbon coating layers can be selected to achieve the desired substrate doping. In certain embodiments, the boron and carbon solid diffusion layer can have a thickness of up to about 5 nanometers (nm). In certain embodiments, the boron and carbon solid diffusion layer can have a thickness of about 4 nanometers or about 3 nanometers. For example, the boron and carbon solid diffusion layer can have a thickness of about 1 nanometer. In certain embodiments, a film stack comprising boron and a carbon solid diffusion layer on a substrate and having no cover layer or substantially no cover layer can have a thickness of less than about 4 nanometers. In certain embodiments, the boron and carbon coating layers can have a thickness of up to about 5 nanometers (including up to about 4 nanometers or about 3 nanometers). For example, the boron and carbon coating layers can have a thickness of about 1 nanometer. In some embodiments, a 1 nanometer thick boron and carbon solid diffusion layer on a substrate and a blanketless or substantially uncoated film stack or a 1 nanometer thick layer on a conventional boron-containing solid diffusion layer The film stack of boron and carbon cap layers can provide the desired doping of the underlying substrate. In certain embodiments, a film stack having a thickness of up to about 4 nanometers and comprising boron and a carbon solid diffusion layer on the substrate and no cover layer or substantially no cover layer, or having a thickness of up to about 4 nanometers and A film stack comprising boron and a carbon cap layer on a conventional boron-containing solid diffusion layer can provide the desired doping of the underlying substrate.

One or more process parameters for the boron and carbon dopant film growth process can be adjusted to achieve desired boron and carbon dopant film characteristics, for example to provide the desired boron concentration in the dopant film to achieve The desired doping of the underlying substrate. One or more process parameters for the boron and carbon dopant film growth process can be adjusted to achieve the desired boron and carbon film thickness to provide the desired doping of the underlying substrate. For example, determining the boron reactant, the duration of the reactant pulse, the duration of the purge step, the process temperature, and/or the number of repetitions of the reactant pulse to provide the desired properties (eg, desired boron and Boron and carbon film of carbon film thickness). In certain embodiments, one or more parameters of one cycle of the reactant pulse and purge step may be different from another cycle (eg, one cycle of the reactant pulse and purge step as described with reference to FIG. 1) One or more parameters to deposit a film having the desired characteristics.

In some embodiments, the thermal annealing process is performed after depositing the boron and carbon film dopant films. For example, a thermal annealing process can be performed after a desired film stack for a solid state doping scheme (eg, a film stack including boron and a carbon solid diffusion layer or a film stack including boron and a carbon cap layer) has been formed. The thermal annealing process drives the boron dopant into the underlying substrate and can be carried out at a process temperature of from about 800 ° C to about 1500 ° C, including from about 800 ° C to about 1200 ° C. In certain embodiments, the annealing process can be performed in an environment comprising nitrogen (N ₂ ) and/or helium (He). In certain embodiments, the thermal annealing process can include hydrogen (H ₂ ). In certain embodiments, the hydrogen (H ₂ ) containing environment can increase the diffusion of boron into the substrate, for example, as compared to a thermal annealing process that does not use hydrogen (H ₂ ). In certain embodiments, the thermal annealing process can have a duration of from about 0.5 seconds to about 5 seconds, including from about 0.5 seconds to about 3 seconds. For example, the thermal annealing process can be performed in a nitrogen-containing environment (eg, an N ₂ environment) at a process temperature of about 1000 ° C for about 1 second. The thermal annealing process can be performed multiple times to achieve the desired boron dopant profile in the underlying substrate. For example, the thermal annealing process can be performed once to achieve the desired dopant profile. For example, the thermal annealing process can be performed twice to achieve the desired dopant profile.

2A and 2B show an example of a film stack including a boron and carbon (BC) film. 2A shows boron and carbon dopant films deposited directly on a germanium substrate. For example, the boron and carbon films may be solid state diffusion (SSD) layers deposited directly onto the germanium substrate, such that the boron and carbon films are subjected to a thermal annealing process to drive boron from the boron and carbon films into the germanium substrate. To provide a dopant to the substrate.

In some embodiments, an undoped layer can be formed on the substrate, and a boron and carbon solid diffusion layer can be formed on the undoped layer. In certain embodiments, the undoped layer can comprise ruthenium oxide. For example, a boron and carbon solid diffusion layer can be deposited on the tantalum oxide layer formed on the tantalum substrate. Without being bound by any particular theory or mode of operation, the undoped layer may facilitate control of substrate doping. For example, forming an undoped yttrium oxide layer on the substrate such that boron and carbon solid diffusion layers are not deposited directly on the substrate can provide a desired boron concentration profile in the substrate after annealing. In certain embodiments, the undoped layer can have from about 0.5 nanometers to about 4 nanometers (including from about 0.5 nanometers to about 3 nanometers, from about 0.5 nanometers to about 2 nanometers, or about 0.5 nanometers). The thickness of the rice to about 1 nm). For example, in certain embodiments, the undoped yttria layer can have a thickness of from about 0.5 nanometers to about 4 nanometers.

As described herein, boron and carbon films can be used as a cover layer in solid state doping. For example, a conventional dopant film can be formed on a substrate and a boron and carbon cap layer can be formed on a conventional dopant film. In some embodiments, the conventional dopant film can be a boron doped film. 2B shows a first boron doped film on a germanium substrate and a different second boron and carbon film on the boron doped film. The first boron doped film may comprise a conventionally shaped boron-containing solid diffusion layer, such as a BSG layer. The second boron and carbon film on the conventionally formed boron doped film may be a cover layer. In certain embodiments, the cap layer inhibits dopant diffusion outward from the underlying boron doped film. For example, a first boron dopant film can be formed directly on the germanium substrate and a second boron and carbon cap layer can be deposited directly onto the boron doped film by a process as described herein. In certain embodiments, boron and carbon capping layers can be deposited on the boron doped film and are not exposed or substantially exposed to ambient air (eg, in processes for depositing boron doped films and for There is no air exposure between the processes for depositing boron and carbon coatings). For example, boron and carbon capping layers can be deposited on the boron doped film in an in situ sequential deposition process. The film stack shown in Figure 2B can be subjected to a thermal annealing process to drive boron from the boron doped film and/or boron and carbon capping layers into the germanium substrate.

FIG. 3 illustrates a flow diagram 200 of another example of a process for forming a boron and carbon (BC) film, in accordance with certain embodiments. In block 202, the substrate is exposed to a boron and carbon film growth process. The boron and carbon film growth process can include a deposition process such as a pulsed thermal CVD process for depositing boron and carbon films having a desired thickness and/or composition. For example, the boron and carbon film growth process can include repeating the cycle of including a reactant pulse followed by a purge step (eg, a reactant pulse and a purge step as described with reference to FIG. 1). The cycle can be repeated multiple times to achieve the desired boron and carbon film thickness and/or composition.

In block 204, a post deposition process can be performed on the deposited boron and carbon films. In certain embodiments, the post deposition processing process includes a plasma process. For example, the processing process can include contacting the deposited boron and carbon film with one or more energized materials for a certain duration. In certain embodiments, the post deposition process includes contacting a substrate comprising boron and a carbon film with a plasma. For example, the substrate can be contacted with a plasma produced using a nitrogen containing compound (eg, nitrogen), an inert gas, and/or an oxygen containing compound (eg, oxygen and/or ozone). In some embodiments, the purge step can be performed after the post deposition process. For example, the purging step can include flowing nitrogen and/or one or more inert gases. In certain embodiments, purging the reactor chamber after the post-deposition treatment process can include: turning off the plasma power while continuing to flow for one or more of the gases used to produce the plasma for the post-deposition treatment process. For example, during the purge step, one or more gases used to produce the plasma for the post-deposition treatment process may be continuously flowed into the reactor while the plasma power is turned off, during the purge step. The flow rate of the one or more gases is the same as or different than the flow rate during the post deposition processing process.

In certain embodiments, exposing the boron and carbon films to a post-plasma deposition process can facilitate, for example, further reducing the treated boron compared to the etch rate of boron and carbon films formed without performing a post-deposition process. And the etching rate of the carbon film. Without being limited by any particular theory or mode of operation, exposing the boron and carbon films to a post-plasma deposition process as described herein increases the density of the boron and carbon films, thereby providing boron compared to untreated boron. And a carbon film that exhibits a reduced etch rate of the treated boron and carbon film. In certain embodiments, the etch rate of a portion of the boron and carbon film deposited on the sidewalls of the three-dimensional structure may exhibit as deposited on the structure after the boron and carbon film are exposed to the post-plasma deposition process. A uniform or substantially uniform etch rate of a portion of the boron and carbon film on the top surface (eg, after exposing the boron and carbon film to a plasma process of a post deposition process, such as compared to a post deposition process) The etch rate of the previous film maintains the etch rate uniformity between the top of the boron and carbon film and its sidewall portions). For example, after the post-plasma deposition process, the ratio of the etch rate of the sidewall portions of the boron and carbon films to the etch rate of the top portions of the boron and carbon films can be less than about 4, including less than about 2, about 1.5. In certain embodiments, the ratio is about 1.

As described herein, in certain embodiments, the post-plasma deposition process can include contacting the deposited boron and carbon film with a nitrogen-containing plasma (eg, contacting the deposited boron and carbon film with nitrogen-containing free radicals). And / or ions). One or more nitrogen-containing compounds can be used to produce a nitrogen-containing plasma, such as a nitrogen-containing compound that does not have hydrogen (H). For example, the post-deposition plasma treatment process may include nitrogen gas (N ₂₎ and high energy substance produced (energetic species).

In certain embodiments, the post-plasma deposition process includes exposing the boron and carbon film to a nitrogen-containing plasma for from about 1 second (s) to about 500 seconds, from 10 seconds to about 300 seconds (including about 10 seconds). The duration to about 100 seconds, or about 10 seconds to about 50 seconds. It can be at a process temperature of from about 100 ° C to about 500 ° C (including from about 200 ° C to about 500 ° C, and from about 200 ° C to about 400 ° C) and from about 0.1 Torr to about 20 Torr (including from about 1 Torr to about 10 Torr) And performing a nitrogen-containing post-plasma deposition process under pressure of about 1 Torr to about 8 Torr. In certain embodiments, the plasma power used to generate the nitrogen-containing plasma can range from about 50 watts (W) to about 2000 watts, including from about 50 watts to about 1000 watts, from about 100 watts to about 400 watts, and About 200 watts to about 400 watts.

In some embodiments, the post-plasma deposition process includes contacting the deposited boron and carbon film with a plasma containing an inert gas (eg, contacting the deposited boron and carbon film with free radicals and/or ions containing an inert gas). ). For example, the post-plasma deposition process can include a plasma comprising energetic materials produced using helium (He) gas, argon (Ar), and/or neon (Ne) gas. In certain embodiments, the post-plasma deposition process includes exposing the boron and carbon film to an inert gas-containing plasma for a duration of from about 10 seconds to about 300 seconds, including from about 10 seconds to about 100 seconds. It can be at a process temperature of from about 100 ° C to about 500 ° C (including from about 200 ° C to about 500 ° C and from about 200 ° C to about 400 ° C) and from about 0.1 Torr to about 20 Torr (including from about 1 Torr to about 10 Torr and A post-plasma deposition process containing an inert gas is performed at a pressure of from about 1 Torr to about 8 Torr. In certain embodiments, the plasma power used to generate the inert gas-containing plasma can range from about 50 watts (W) to about 2000 watts, including from about 50 watts to about 1000 watts, from about 100 watts to about 400 watts, And about 200 watts to about 400 watts.

In some embodiments, the post-plasma deposition process includes contacting the deposited boron and carbon film with an oxygen (O)-containing plasma (eg, contacting the deposited boron and carbon film with oxygen-containing free radicals and/or ion). In certain embodiments, oxygen-containing compounds such as oxygen (O ₂ ) and/or ozone (O ₃ ) may be used to produce an oxygen-containing plasma. In certain embodiments, the post-plasma deposition process can include exposing the boron and carbon film to the oxygen-containing plasma for a duration of from about 10 seconds to about 300 seconds, including from about 10 seconds to about 100 seconds. It can be at a process temperature of from about 100 ° C to about 500 ° C (including from about 200 ° C to about 500 ° C, and from about 200 ° C to about 400 ° C) and from about 0.1 Torr to about 20 Torr (including from about 1 Torr to about 10 Torr) An oxygen-containing post-plasma deposition process is performed at a pressure of from about 1 Torr to about 8 Torr. In certain embodiments, the plasma power used to generate the oxygen-containing plasma can range from about 50 watts (W) to about 2000 watts, including from about 50 watts to about 1000 watts, from about 100 watts to about 400 watts, and About 200 watts to about 400 watts.

In certain embodiments, the post-deposition treatment process of the oxygen-containing plasma (eg, using oxygen and/or ozone) can increase the refractive index of the boron and carbon films. In certain embodiments, the oxygen-containing post plasma deposition process can reduce the thickness of the boron and carbon films (eg, the thickness of the treated film can be less than the thickness of the film prior to exposure to the post deposition process) ). Without being bound by any particular theory or mode of operation, exposure of the boron and carbon films to the oxygen-containing plasma may facilitate replacement of the hydrogen (H) and/or carbon (C) components of the membrane with oxygen (O), for example A film containing BO _x is produced. Further not limited by any particular theory or mode of operation, variations in the composition of the boron and carbon films (eg, replacement of the hydrogen (H) and/or carbon (C) components of the film with oxygen (O)) may be by the film. reduction and / or decreasing the refractive index of the film thickness (e.g., by increasing the film density and / or remove volatile substances BO _x) to reflect. For example, exposure of boron and carbon films to oxygen-containing plasma under certain conditions can result in complete or substantially complete removal of the deposited boron and carbon films (eg, plasma for boron and carbon films). Etching).

In some embodiments, the post-plasma deposition process can be performed once after depositing boron and carbon films having the desired thickness and/or composition. In certain embodiments, after each repetition of multiple cycles of a deposition process for depositing boron and carbon films (eg, in a cycle of reactant pulses and purge steps as described with reference to FIG. 1) A post-plasma deposition process is performed at intervals of multiple repetitions. For example, a post-plasma deposition process can be performed after every 1, 2, 5, 10, 100, 1,000 cycles of the boron and carbon film deposition process. Other numbers of cycles may also be suitable. In some embodiments, the number of cycles of the process for depositing boron and carbon films is a ratio of the number of cycles used to form a post-plasma deposition process with boron and carbon films having desired characteristics (eg, Y:X) The ratio) can range from about 5,000:1 to about 1:1, including from about 2,000:1 to about 50:1. In certain embodiments, the ratio of the number of cycles of the process of depositing the boron and carbon films to the number of cycles of the post-plasma deposition process can range from about 1,500:1 to about 1:1, including from about 1,000:1 to about 1: 1. From about 500:1 to about 1:1, from about 100:1 to about 1:1, from about 50:1 to about 1:1, and from about 20:1 to about 1:1.

In some embodiments, one or more parameters of the post-plasma deposition process can be adjusted to facilitate the formation of boron and carbon films having desired characteristics. For example, the duration of the process, plasma power, pressure, plasma composition, and/or number of iterations can be selected to facilitate the production of boron and carbon films having the desired etch characteristics.

Suitable reaction chambers for one or more of the boron and carbon (BC) film deposition processes described herein can be part of a clustering tool in which various processes in the formation of integrated circuits are performed. In certain embodiments, it may be in a batch processing reactor (including, for example, in a mini batch reactor (eg, a reactor having a capacity of 8 substrates or less than 8 substrates) and/or batching in a furnace Processing the reactor (eg, a reactor having a capacity of 50 or more than 50 substrates) performs one or more of the boron and carbon film deposition processes described herein. In certain embodiments, one or more of the boron and carbon film deposition processes described herein can be performed in a single wafer reactor. In certain embodiments, a space reactor chamber may be suitable. In certain embodiments, a reactor chamber having a cross-flow configuration may be suitable (eg, to provide a gas flow that is parallel or substantially parallel to the surface of the substrate located in the reactor chamber). Reactor chamber). In certain embodiments, a reactor chamber having a showerhead configuration can be a suitable (eg, a reactor chamber to provide a gas flow that is perpendicular or substantially perpendicular to the surface of the substrate located in the reactor chamber). ).

In some embodiments, the boron and carbon films used as dopant films are not subjected to post-plasma deposition processing. For example, boron and carbon dopant films may not be subjected to one or more post-plasma depositions as described herein prior to subsequent processing, such as prior to the thermal annealing process used to drive dopants into the underlying substrate. Process the process.

An exemplary single wafer reactor is commercially available under the tradenames Pulsar® 2000 and Pulsar® 3000 from ASM America, Inc. of Phoenix, AZ, and under the trade name Eagle® (Eagle®). XP and Eagle® XP8 are commercially available from ASM Japan, Inc. of Tokyo, Japan. Exemplary batch processing ALD reactors are commercially available from ASM Europe, Almere, Netherlands, under the tradenames A400 ^(TM) and A412 ^(TM ).

BC film example

4 is a graph of growth rate (in angstroms per cycle) versus process temperature (in degrees Celsius) of boron and carbon (BC) films deposited in accordance with certain embodiments. The boron and carbon (BC) films shown in Figure 4 were deposited using a pulsed thermal CVD process in a Pulsar® 3000 reactor chamber with a cross-flow configuration. One cycle of the pulsed thermal CVD process includes a reactant pulse having a duration of about 0.5 seconds, and a subsequent purge step having a duration of about 5 seconds. The reactant pulse includes supplying TEB and nitrogen into the reactor chamber. The TEB is supplied to the reactor chamber by a vapor extraction process by providing a gasified TEB from a source vessel maintained at a temperature of about 20 °C. The pressure in the reactor chamber during the reactant pulse is maintained from about 0.1 Torr to about 10 Torr. The purge step includes flowing nitrogen through the reactor chamber. The growth rates of boron and carbon films deposited according to a pulsed thermal CVD process were measured at process temperatures of about 375 ° C, about 400 ° C, and about 450 ° C. As shown in FIG. 4, the growth rate of boron and carbon films per cycle increases as the process temperature increases. As shown in FIG. 4, the boron and carbon films deposited by such a pulsed thermal CVD process can have a linear or substantially linear relationship with the process temperature.

The composition of boron and carbon (BC) films deposited according to the process described with reference to FIG. 4 at a process temperature of about 400 ° C was measured by rutherford backscattering spectrometry (RBS) and found The boron and carbon film composition has a boron and carbon stoichiometry of about B _0.608 C _0.392 or B _1.5 C. The refractive indices of the boron and carbon films deposited according to the process described with reference to FIG. 4 at a process temperature of about 400 ° C were measured by spectroscopic ellipsometry. The refractive index was found to be about 1.98 at a wavelength of about 633 nanometers (nm). Wet etch rate performance of a film deposited according to the process described with reference to Figure 4 at a process temperature of about 400 ° C in a dilute hydrofluoric acid solution (eg, 0.5 wt% aqueous HF solution) was measured and found The membrane unexpectedly tolerated the diluted HF solution. It has been found that the wet etch rate in the diluted HF solution is negligible, for example, after exposure to the diluted HF solution for up to about 10 minutes (eg, immersed in dHF for up to about 10 minutes). In certain embodiments, a negligible etch rate is observed after exposure for up to about 30 minutes or longer exposure. The wet etch rate of the films in the dilute hydrofluoric acid solution was found to be less than 0.3 times the etch rate of hot yttrium oxide (TOX).

Figure 5 shows a Fourier Transform Infrared Spectroscopy (FTIR) analysis of boron and carbon (BC) films deposited according to the process described with reference to Figure 4 at a process temperature of about 400 °C. FTIR analysis revealed the presence of CH bonds, BH bonds, BC bonds, BB bonds, and CC bonds in boron and carbon films. For example, a peak at about 2902 cm ^-1 can contribute to the CH bond, and a peak at about 2573 cm ^-1 can contribute to the BH bond in the film. The peak at 1201 cm ^-1 and the peak at 1051 cm ^-1 indicate the presence of the BC bond, the BB bond, and the CC bond.

Boron and carbon (BC) films were deposited on a blanket wafer having a diameter of about 300 millimeters (mm) at a process temperature of about 400 °C using a process as described with reference to FIG. Deposition was performed in a Pulsar® 3000 reactor chamber with a cross-flow configuration. After applying 1,000 cycles of the pulsed thermal CVD process shown in Fig. 4, the average film thickness was measured to be about 35.58 nm. The deposited boron and carbon films show, for example, the edge of the wafer, such as the leading edge of the wafer (eg, a portion of the wafer edge that is further from the wafer recess), increasing toward the center of the wafer. Without being limited by any particular theory or mode of operation, such a thickness profile may be indicative of a surface reaction limited growth mechanism, and thickness variations may result from temperature changes in the susceptor where the wafer is positioned. Surface-restricted growth can advantageously promote improved film conformal performance of boron and carbon films deposited on 3-D features.

Boron and carbon (BC) films were deposited on blanket wafers in a Pulsar® 3000 reactor chamber with a cross-flow configuration at a process temperature of about 450 °C. After 1,000 cycles of applying the pulsed thermal CVD process shown in Figure 4, the average thickness of the deposited boron and carbon films was about 81.88 nm. The film deposited at about 450 ° C exhibits an increased thickness compared to boron and carbon films deposited at about 400 ° C. The deposited boron and carbon films have, for example, an increased thickness closer to the leading edge of the blanket wafer than the boron and carbon films deposited at 400 °C. Without being limited by any particular theory or mode of operation, the increased thickness near the leading edge may be indicative of a mass-transport limited film growth mechanism as opposed to a surface reaction limited growth mechanism.

6A-6D are scanning electron microscopy (SEM) showing a cross-sectional view of a boron and carbon (BC) film deposited on a high aspect ratio trench structure 500 using a deposition process as described with reference to FIG. image. Boron and carbon films were deposited at a process temperature of about 400 ° C, in a Pulsar® 3000 reactor chamber, and by applying 1,500 cycles of reactant pulses as described with reference to Figure 4 and subsequent purge steps. Figure 6A shows an SEM image of a high aspect ratio trench structure 500 at 15k x magnification. Figure 6B shows an SEM image of the upper portion 502 of the high aspect ratio trench structure 500 at 100k x magnification. 6C shows an SEM image of the intermediate section 504 of the high aspect ratio trench structure 500 at 100k× magnification, and FIG. 6D shows an SEM image of the lower portion 506 of the high aspect ratio trench structure 500 at 100k× magnification. . The thicknesses of the deposited boron and carbon films in each of the upper, middle, and lower portions of the high aspect ratio trench structure are shown in FIGS. 6B, 6C, and 6D, respectively. As shown in FIG. 6, a relatively uniform film thickness is achieved on each side of the high aspect ratio trench structure at the upper, middle, and lower portions of the trench structure, for example, to confirm the enhanced total of deposited boron and carbon films. Formality. For example, a film thickness of about 72 nm is measured in the upper portion 502 of the high aspect ratio trench structure 500, and a film thickness of about 69 nm is measured at the intermediate portion 504 of the trench structure 500, and in the trench. A film thickness of about 69 nm was measured at the lower portion 506 of the structure 500, for example, to confirm that a conformality of greater than or equal to about 95% was achieved. Without being limited by any particular theory or mode of operation, the deposition of boron and carbon films at process temperatures of about 400 ° C or below may facilitate deposition of the film in a surface reactive constrained system to facilitate deposition. The conformality of the film.

Figure 7 is a graph showing the removal rates of various boron and carbon (BC) films when exposed to 0.5 wt% HF solution (diluted HF solution) as a function of the number of deposition cycles used to form the corresponding boron and carbon films. The graph. The y-axis shows the thickness (in angstroms (Å)) of the film removed after exposure of the boron and carbon film to the diluted HF for about 60 seconds. The x-axis shows the number of deposition cycles used to form the corresponding boron and carbon films, and the removal of boron and carbon films deposited using 1 cycle, 10 cycles, 20 cycles, and 30 cycles was measured. rate. The etching performance of boron and carbon films deposited on four different substrates after exposure to diluted HF is shown. The etching performance curve A in FIG. 7 corresponds to boron and carbon films deposited on tantalum nitride (SiN) formed by a low process temperature process. The etching performance curve B corresponds to boron and carbon films deposited on natural cerium oxide. The etching efficiency C corresponds to a boron and carbon film deposited on aluminum nitride (AlN), wherein the aluminum nitride is subjected to air interruption after forming aluminum nitride and before depositing boron and carbon film on the aluminum nitride (air) Break). The etching performance curve D of FIG. 7 corresponds to boron and carbon films deposited on aluminum nitride (AlN), wherein aluminum nitride is not formed after aluminum nitride is formed and before boron and carbon films are deposited on aluminum nitride. Withstanding air interruptions.

The boron and carbon films shown in Figure 7 were deposited in a batch reactor having 120 wafer loads. The film is deposited by supplying a corresponding number of deposition cycles to the reactor chamber. Both of circulating boron, and each carbon deposition process comprises a boron precursor and the pulse has a duration of about 5 seconds, wherein said boron comprises TEB pulse precursor and a nitrogen gas (N ₂₎ flow into the reactor chamber Nitrogen (N ₂ ) was used as an inert carrier gas. Each cycle is performed at a process temperature of about 350 ° C and includes a purge step after the boron precursor pulse. The purge step has a duration of about 18 seconds, and comprises nitrogen (N ₂₎ flow into the reactor chamber.

As shown in FIG. 7, the boron and carbon films generally exhibit increased resistance to removal by dilution of HF as the number of deposition cycles used to form the film increases. Boron and carbon films deposited on low temperature process yttrium oxide using 10 deposition cycles and above 10 deposition cycles exhibited resistance to removal by exposure to diluted HF for 60 seconds. At the same time, boron and carbon films deposited on natural cerium oxide using 20 deposition cycles and above 20 deposition cycles exhibited resistance to removal by exposure to diluted HF for 60 seconds. Boron and carbon films deposited on aluminum nitride subjected to air interruption using 20 deposition cycles and more than 20 deposition cycles exhibited resistance to removal by exposure to diluted HF for 60 seconds, At the same time, boron and carbon films were deposited on the aluminum nitride which was not interrupted by air using 30 deposition cycles which exhibited resistance to removal by exposure to diluted HF for 60 seconds.

Figure 8 is a graph showing the deposition rate of boron and carbon (BC) films as a function of process temperature, wherein the reactant pulses for the deposition process comprise TEB and argon. The deposition rate in nanometers per minute (nm/min) is shown on the y-axis and the process temperature in degrees Celsius corresponding to each plotted deposition rate is shown on the x-axis. Using pulsed thermal CVD processes boron and carbon as shown in Eagle ^® 12 8 in FIG deposition reactor. One cycle of the pulsed thermal CVD process includes a reactant pulse having a duration of about 0.3 seconds and a subsequent purge step having a duration of about 1 second. The reactant pulse includes supplying TEB and argon to the reactor chamber. The TEB is supplied to the reactor chamber by a vapor extraction process by providing a gasified TEB from a source vessel maintained at a temperature of about 20 °C. The pressure in the reactor chamber during the reactant pulse is maintained from about 0.1 Torr to about 10 Torr. The purge step includes flowing argon through the reactor chamber. The growth rates of boron and carbon films deposited according to a pulsed thermal CVD process were measured at process temperatures of about 350 ° C, about 400 ° C, about 420 ° C, and about 430 ° C. As shown in Figure 8, the growth rate of boron and carbon films per cycle increases as the process temperature increases. As shown in FIG. 8, boron and carbon films deposited by such a pulsed thermal CVD process using TEB and argon may have a nonlinear relationship with process temperature. For example, the film growth rate at a process temperature of about 430 ° C is significantly higher than film growth at a process temperature of about 350 ° C. In certain embodiments, such boron and carbon films can be dopant films including boron and carbon solid diffusion layers and/or capping layers.

9A shows a scanning transmission electron microscopy at 180 k× magnification of a cross-sectional view of boron and carbon films deposited using the process described above with reference to FIG. 8 at a process temperature of about 430 ° C. STEM) image. The boron and carbon films exhibit conformal coverage of the trench features. As shown in Figure 9A, boron and carbon films are deposited directly onto the substrate.

Figure 9B is a table providing the composition of the boron and carbon (BC) films shown in Figure 9A. As shown in the table, boron and carbon films mainly contain boron, carbon and hydrogen. The boron and carbon films comprise about 35 atomic percent boron (B), about 33 atomic percent carbon (C), about 28 atomic percent hydrogen (H), about 2 atomic percent nitrogen (N), and about 2 atomic percent. Oxygen (O).

Figure 10 is a graph showing the boron concentration at various depths in the tantalum layer after annealing the boron and carbon films deposited on the tantalum layer by the above process. The boron concentration was measured by Secondary Ion Mass Spectrometry (SIMS). The boron concentration in atomic/cubic centimeters (atoms/cm ³ ) is shown on the y-axis, and the depth measured in the nanometer (nm) from the top surface of the tantalum layer is shown on the x-axis. Boron and carbon films having a thickness of about 1 nm were deposited directly on the tantalum substrate at a process temperature of about 415 ° C using the process described with reference to FIG. The film stack including the boron and carbon solid diffusion layers was then subjected to a thermal annealing process performed at a process temperature of about 1000 ° C for a duration of about 1 second in a nitrogen (N ₂ ) environment.

As shown in FIG. 10, a 1 nm thick boron and carbon solid diffusion layer was used to achieve a boron concentration or doping level of about 2E+20 atoms/cm 3 at the surface of the tantalum substrate. The boron concentration achieved using boron and carbon solid diffusion layers is significantly higher than the conventional solid diffusion layer and conventional cover layer (for example, 3 nm dioxide on a 1 nm boronic acid glass (BSG) solid diffusion layer) Boron concentration obtained by 矽 coating). For example, boron concentrations achieved using boron and carbon solid diffusion layers are significantly higher than boron concentrations obtained using conventional solid diffusion layers and conventional overlays having depths up to about 40 nanometers.

Figure 11 is a graph showing aging analysis of boron and carbon films by Fourier transform infrared spectroscopy (FTIR). Boron and carbon films were deposited using a process described with reference to Figure 8 at a process temperature of about 415 °C. FTIR analysis was performed on the film for about seven days after deposition of the boron and carbon films. Exposure of boron and carbon film to ambient air (eg, around the clean room) for a duration of seven days.

The FTIR analysis shown in Figure 11 shows that the characteristics of the boron and carbon films remain unchanged or substantially constant over a period of about 7 days, thus exhibiting the desired chemical stability after deposition. For example, FTIR analysis shows that the film does not absorb a significant amount of moisture from the air. Boron and carbon films that can exhibit the desired stability after deposition (eg, exhibit negligible absorption of moisture when exposed to ambient air) can be used as a cover layer in solid state doping schemes. As described herein, boron and a carbon cap layer can be deposited onto a conventional solid diffusion layer, such as a borosilicate glass (BSG) layer, to provide the desired doping of the semiconductor substrate. Without being limited by any particular theory or mode of operation, boron and carbon films that exhibit negligible absorption of moisture when exposed to ambient air can be used as a solid diffusion layer without a cover layer or substantially a cover layer.

Figure 12 is a table showing optical properties and deposition performance of examples of boron and carbon films deposited by the process described with reference to Figure 8 at a process temperature of about 415 °C. The film was subjected to thermal annealing under a nitrogen (N ₂ ) atmosphere for a duration of about 1 second at a process temperature of about 1000 °C. As shown in the table, the deposition process provides a deposition rate of about 0.045 nm/cycle and about 2.091 nm/min. The 1 sigma (1σ) unevenness of the deposited film was about 18.42%.

The refractive indices of boron and carbon films are measured by a spectroscopic ellipsometer. As shown in the table of FIG. 12, the film exhibited an average refractive index of about 1.805 at a wavelength of about 633 nanometers (nm).

Boron nitride film containing boron and carbon

As described herein, a tantalum nitride film comprising boron and a carbon component can be deposited, and a tantalum nitride film comprising boron and a carbon component can have various applications, including applications in the fabrication of semiconductor devices. Deposition of a tantalum nitride film having desired characteristics at a reduced temperature (eg, at a temperature of less than about 500 ° C) using atomic layer deposition (ALD), for example, to provide a process with reduced thermal budget For the sake of difficulty. A tantalum nitride film deposited by a conventional process at a lower process temperature provides a film having poor film quality and a three-dimensional (3-D) structure on which a lanthanide film is deposited. Poor film conformality, undesirably high dry etch rate, and/or undesirably low etch selectivity (eg, etch selectivity to another material in a semiconductor device, including thermal yttrium oxide materials), The tantalum nitride film can be subjected to one or more subsequent thermal ruthenium oxide etching steps used in the device fabrication process.

For convenience and simplicity, the chemical formula of the tantalum nitride film is commonly referred to herein as SiN. However, those skilled in the art will appreciate that the actual chemical formula of tantalum nitride can be SiNx, where x varies from about 0.5 to about 2.0, as long as certain Si-N bonds are formed. In certain instances, x is preferably from about 0.9 to about 1.7, more preferably from about 1.0 to about 1.5, and most preferably from about 1.2 to about 1.4. A tantalum nitride in which Si has an oxidized state of +IV is generally formed, and the amount of nitride in the material may vary.

For convenience and simplicity, the chemical formula of a tantalum nitride film comprising boron and carbon components is commonly referred to herein as SiN (B, C). However, those skilled in the art will appreciate that the actual chemical formula of SiN(B, C) can be SiN _x (B _y , C _z ). In certain embodiments, for example, x can vary from about 0.5 to about 3.0 as long as certain Si-N bonds are formed. In certain instances, x preferably varies from about 1.0 to about 2.0 and more preferably from about 1.3 to about 1.8. In certain embodiments, y can be between about 0.1 and about 5.0, including preferably from about 0.3 to about 3.0, and more preferably from about 0.5 to about 1.5. For example, y can be about 1.5. In certain embodiments, z can be from about 0.1 to about 5.0, including preferably from about 0.2 to about 2.5, and more preferably from about 0.3 to about 1.3. For example, z can be about 1.0.

One or more of the methods described herein can include an atomic layer deposition (ALD) process and/or a chemical vapor deposition (CVD) process, and can be used to form a tantalum nitride film, such as tantalum nitride containing boron and carbon components. Membrane SiN (B, C). In certain embodiments, the tantalum nitride film comprising boron and carbon components has improved conformal coverage of three-dimensional (3-D) features, a desired dry etch rate, a desired wet etch rate, and/or One or more of the desired etch selectivity to another material, such as a thermal yttrium oxide layer (TOX) in a semiconductor device. For example, a tantalum nitride film comprising boron and a carbon component deposited according to one or more processes described herein (eg, for use in, for example, a semiconductor transistor (including, for example, a fin field effect transistor) Applications of barrier features such as gate features in a transistor) can exhibit increased step coverage, reduced etch rate in wet etchants (eg, for example, diluted hydrofluoric acid (HF or DHF) resistance of a wet etchant such as a solution (eg, 0.5% by weight of HF solution), and/or reduced wet etch rate to a thermal yttrium oxide material (eg, wet type of tantalum nitride film) The ratio of etch rate to wet etch rate of the thermal yttrium oxide material is less than about 1, including less than about 0.5). In certain embodiments, a tantalum nitride film comprising boron and a carbon component can have a desired dielectric constant (kappa-value), such as a dielectric constant of less than about 7 (including less than about 6 and less than about 5.5). For example, a tantalum nitride film comprising boron and a carbon component can have a dielectric constant between about 4.8 and about 6, including between about 4.8 and about 5.5.

In some embodiments, a tantalum nitride ALD deposition process can be used to deposit a tantalum nitride (SiN) film having a desired thickness and composition. The ALD type process is based on a controlled self-limiting surface reaction. The gas phase reaction is avoided by alternately and sequentially contacting the substrate with the reactants. The gas phase reactants are separated from one another in the reaction chamber, for example by removing excess reactants and/or reactant by-products from the reaction chamber between reactant pulses. For example, an ALD deposition process can include contacting a substrate with a ruthenium reactant such that the ruthenium reactant adsorbs on the surface of the substrate, and subsequently contacting the substrate with the nitrogen reactant. The ruthenium reactant may comprise a ruthenium containing compound that contributes to the growth of the tantalum nitride film. The nitrogen reactant may comprise a nitrogen-containing compound that contributes nitrogen to the growth of the tantalum nitride film. Exposure of the substrate to the ruthenium reactant and the nitrogen reactant can be repeated as many times as necessary to achieve a film having the desired thickness and composition. After each contacting step, excess reactant can be removed from the vicinity of the substrate, for example by purging the reaction space with an inert gas. For example, the reactor chamber can be purged between reactant pulses. The flow rate and time of each reactant are fine tunable, as is the purge step to allow control of the dopant concentration and depth profile in the film. In certain embodiments, the substrate can be moved to a non-reactant or substantially non-reactive space prior to purging to remove excess reactants and/or reaction byproducts from the reactor chamber.

In certain embodiments, an ALD process for depositing a tantalum nitride (SiN) film can include one or more cycles, each cycle including at least two distinct processes or stages. Providing and removing reactants from the reaction space can be considered a stage. In a first process or stage, a first reactant comprising ruthenium is provided and the first reactant forms up to about one monolayer on the surface of the substrate. This reactant is also referred to herein as "矽 precursor" or "矽 reactant". In a second process or stage, a second reactant comprising a nitrogen-containing compound is provided, and the second reactant reacts with the adsorbed ruthenium precursor to form SiN. This second reactant may also be referred to as a "nitrogen precursor" or a "nitrogen reactant." As described herein, the second reactant may comprise an ammonia (NH ₃₎ and / or another suitable nitrogen-containing compounds. Additional processes or stages may be added as needed, and the stage of removal may be adjusted as needed to adjust the composition of the final film. In certain embodiments for depositing a tantalum nitride (SiN) film, one or more deposition cycles typically begin with providing a hafnium precursor and then providing a nitrogen precursor. In certain embodiments, one or more deposition cycles begin by providing a nitrogen precursor and then providing a ruthenium precursor. One or more of the reactants may be provided by means of a carrier gas such as nitrogen (N ₂ ), argon (Ar), and/or helium (He).

In certain embodiments, the process for depositing a tantalum nitride (SiN(B,C)) film comprising boron and carbon components and having desirable characteristics can include a hybrid process including both an ALD process and a CVD process. For example, a process for forming a tantalum nitride film comprising boron and a carbon component can include an ALD portion for depositing tantalum nitride and a CVD portion for bonding boron and a carbon component into the grown film. In certain embodiments, tantalum nitride and boron and carbon components can form a continuous film in which tantalum nitride and boron and carbon components do not form distinct layers or substantially do not form distinct layers.

In certain embodiments, no plasma is used in the deposition of a tantalum nitride film comprising boron and a carbon component. For example, the process for depositing a tantalum nitride film comprising boron and carbon components can include both thermal ALD processes and thermal CVD processes, including pulsed thermal CVD processes. In some embodiments, a plasma of a nitrogen precursor is used in an ALD process for depositing tantalum nitride. For example, a plasma-enhanced atomic layer deposition (PEALD) process using a plasma containing a nitrogen precursor can be used to deposit tantalum nitride, and the PEALD process can be used to convert boron and carbon. The components are combined in a thermal CVD process incorporated into tantalum nitride.

In certain embodiments, a process for depositing a tantalum nitride (SiN(B,C)) film comprising boron and a carbon component can include the following process: an ALD process for depositing a tantalum nitride (SiN) film ( For example, comprising alternately and sequentially contacting the substrate with a ruthenium reactant (eg, comprising octachlorotrioxane (Si ₃ Cl ₈ , OCTS)) and a nitrogen reactant (eg, an ALD process comprising ammonia (NH ₃ )), And a decomposition process in which one or more boron reactants decompose on the surface of the substrate to introduce boron and carbon components into the tantalum nitride film (eg, using one or more boron reactants (eg, comprising triethyl boron (B ( C ₂ H ₅ ) ₃ , TEB)) and a CVD process in which TEB is decomposed). In certain embodiments, an ALD process for depositing a SiN film can include contacting a substrate with a ruthenium reactant comprising hexachlorodioxane (Si ₂ Cl ₆ , HCDS). In some embodiments, the CVD process for introducing boron and carbon components can include contacting the substrate with, for example, trimethylboron (B(CH ₃ ) ₃ , TMB) or triethylboron (TEB). A boron reactant of an alkyl boron. In certain embodiments, excess may be removed by a purge step after each process (eg, the purge step may be performed after a helium reactant pulse, a nitrogen reactant pulse, and/or a boron reactant pulse) Reactants and/or reaction by-products. For example, excess ruthenium reactants and/or reaction by-products may be removed from the reaction space prior to introduction of the nitrogen reactant such that the nitrogen reactant reacts with the adsorbed ruthenium reactant to form a single layer of tantalum nitride on the substrate. . In certain embodiments, the substrate can be moved to a non-reactant or substantially non-reactive space prior to purging the reaction space.

In some embodiments, a pulsed CVD process is used for the decomposition process. In some embodiments, a pulsed CVD process in which multiple short pulses of boron reactant are provided is used. In certain embodiments, a single, longer pulse of boron reactant is provided. In certain embodiments, the conditions are selected to form SiN by surface reaction (ALD) under the same conditions while decomposing (CVD) the boron reactant. In certain embodiments, a pulsed CVD process for introducing boron and carbon components into a SiN film facilitates integration of the boron carbon process. In certain embodiments, a pulsed CVD process for introducing boron and carbon components into a SiN film facilitates enhanced control of the amount of boron and carbon components incorporated into the SiN film. In certain embodiments, the boron reactant can also be provided under ALD conditions.

According to some embodiments of the invention, the pressure of the reaction chamber during the treatment is maintained from about 0.01 Torr to about 50 Torr, preferably from about 0.1 Torr to about 10 Torr.

One or more parameters of the process for depositing the tantalum nitride film and/or the process for introducing boron and carbon components can be adjusted to provide a film having the desired characteristics. For example, the flow rate of one or more boron reactants and/or the process temperature of the CVD process for introducing boron and carbon components can be adjusted. For example, the duration of the reactant pulses used to provide one or more boron reactants in a pulsed CVD process can be adjusted. In some embodiments, one or more parameters of the ALD process used to deposit the SiN film can be adjusted, such as process temperature, reactor chamber pressure, and/or reactant exposure duration.

In certain embodiments, the process for depositing a tantalum nitride film comprising boron and a carbon component can include one or more cycles of a process for providing a tantalum nitride (SiN) film (eg, a repeated SiN process) And/or one or more cycles of the process for introducing boron and carbon components (eg, a re-boron carbon process). In some embodiments, the number of repetitions of the SiN process and the number of repetitions of the boron carbon process can be fine tuned to provide a film having the desired characteristics. In some embodiments, the ratio of the number of repetitions of the SiN process to the number of repetitions of the boron carbon process is selected to produce the desired film composition. In certain embodiments, the SiN process cycle is repeated 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, or more for each boron carbon process cycle. repeatedly. In some embodiments, after repeated multiple repetitions of the SiN process cycle, multiple repetitions of the boron carbon process cycle, wherein the number of repetitions of the SiN process cycle is different from the number of repetitions of the boron carbon process cycle.

In certain embodiments, the process for depositing a tantalum nitride film comprising boron and a carbon component can include multiple iterations including an ALD process for depositing a tantalum nitride (SiN) film and/or for introduction Total repetition of the sequence of multiple repetitions of the CVD process for boron and carbon components, the number of repetitions of each of the ALD process, the CVD process, and/or the ordering of both the ALD process and the CVD process The number of times is selected to provide a film having the desired characteristics and/or the desired boron and carbon component composition. For example, the boron and carbon content can be adjusted to provide a film having the desired etch efficiency (eg, wet etch rate and/or dry etch rate) and/or conformal performance. In some embodiments, the number of repetitions of the CVD process can be selected based on one or more parameters of the CVD process and/or the ALD process. In some embodiments, the number of repetitions of the ALD process can be selected based on one or more parameters of the ALD process and/or CVD process. In some embodiments, the multiple repeats of the multiple repeat and CVD process cycles including the ALD process cycle can be repeated to provide a film having the desired composition and/or thickness.

In certain embodiments, the process for depositing a tantalum nitride film comprising boron and a carbon component does not include a plasma enhanced process. That is, no plasma is used throughout the process. For example, the process can include both thermal ALD processes and pulsed thermal CVD processes (eg, thermal decomposition of one or more boron reactants, such as decomposition of TEB).

13 is a flow diagram of an example of a process flow 700 for forming a tantalum nitride film (eg, a SiN (B, C) film) comprising boron and a carbon component. In block 702, the substrate can be exposed to one or more gas phase ruthenium reactants (eg, one or more ruthenium precursors). A layer of ruthenium reactant is formed on the surface of the substrate. In certain embodiments, the one or more gas phase ruthenium reactants can be adsorbed onto the surface of the substrate. In certain embodiments, the one or more ruthenium reactants are at least partially decomposed at the surface of the substrate. In block 704, the substrate can be exposed to one or more gas phase nitrogen reactants (eg, nitrogen precursors). For example, the one or more nitrogen reactants can interact with the one or more ruthenium reactants on a surface of the substrate (eg, the one or more nitrogen reactants can be on the surface of the substrate with the one or A plurality of ruthenium reactants react to form tantalum nitride (SiN). In block 706, the substrate can be exposed to one or more fumed boron reactants (eg, one or more boron and/or carbon precursors). The one or more boron reactants may react with the tantalum nitride on the surface of the substrate, thereby introducing boron and a carbon component into the film to form a tantalum nitride film comprising boron and a carbon component. In certain embodiments, the one or more boron reactants decompose on the surface of the substrate.

In certain embodiments, one or more of the reactants can be at least partially decomposed on the surface of the substrate. For example, one or more of a ruthenium reactant, a nitrogen reactant, or a boron reactant is provided under chemical vapor deposition (CVD) conditions.

In certain embodiments, the process for exposing the substrate to the ruthenium reactant, the nitrogen reactant, and/or the boron reactant can include a chemical vapor deposition (CVD) process. In some embodiments, exposing the substrate to the ruthenium reactant, exposing the substrate to the nitrogen reactant, and exposing the substrate to the boron reactant can each comprise a CVD process, including, for example, a pulsed CVD process.

In certain embodiments, exposing the substrate to the ruthenium reactant, the nitrogen reactant, and/or the boron reactant can include vapor phase deposition in which one or more reactants are decomposed to facilitate formation of a SiN (B, C) film. Process.

In some embodiments, the ALD and/or CVD process can be a plasma enhanced process (eg, direct plasma process and/or remote plasma process). In certain embodiments, the ALD and/or CVD process does not include a plasma enhanced process. For example, the ALD process can be a thermal ALD process.

In certain embodiments, the processes for exposing the substrate to the ruthenium reactants, nitrogen reactants, and/or boron reactants may overlap or combine. For example, one or more of the ruthenium reactants, nitrogen reactants, and/or boron reactants may be provided with pulses that are partially or completely overlapping.

In certain embodiments, a nitrogen-containing gas (eg, nitrogen (N ₂ ) and/or ammonia (NH ₃ )) may be continuously fed throughout the process for depositing the SiN (B, C) film (eg, The nitrogen-containing gas can be used as a carrier gas and/or a reactant. For example, a nitrogen-containing gas can be used as a carrier gas for the reactants in a plasma process (eg, for producing a nitrogen-containing plasma). In certain embodiments, the nitrogen-containing gas is continuously or substantially continuously fed into the reaction chamber throughout the deposition process, including, for example, simultaneously introducing reactant reactants of the ruthenium reactant and/or boron reactant to the reactor chamber. in. The nitrogen-containing gas flow rate and/or the concentration of the nitrogen stream can be adjusted during the deposition process (e.g., during the pulsed supply of the ruthenium reactant and/or boron and/or carbon reactants).

Various hydrazine reactants may be suitable. In certain embodiments, suitable ruthenium reactants in the process for depositing a tantalum nitride film may comprise hafnium halide, decylamine, decylamine, and/or decane (eg, including one or more alkyl groups) At least one of the decanes. For example, a suitable ruthenium reactant can comprise ruthenium chloride. In certain embodiments, the ruthenium reactant can comprise halosilane. In certain embodiments, the ruthenium reactant can comprise a halide containing alkyl hydrazine compound. In certain embodiments, the ruthenium reactant can be an alkyl decane. In certain embodiments, the ruthenium reactant may comprise octachlorotrioxane (Si ₃ Cl ₈ , octachlorotrisilane, OCTS). In certain embodiments, the reaction product may comprise silicon hexachlorodisilane Silane _{(Si 2 Cl 6, hexachlorodisilane,} HCDS).

Suitable nitrogen reactants can include various nitrogen-containing reactants. In certain embodiments, the nitrogen reactant can comprise hydrogen (NH) bonded to nitrogen. In certain embodiments, suitable nitrogen reactant may be ammonia (NH _3). In certain embodiments, a suitable nitrogen reactant can be hydrazine (N ₂ H ₄ ). In certain embodiments, a suitable nitrogen reactant can comprise one or more reactive species produced by a nitrogen-containing plasma, including, for example, nitrogen-containing free radicals. In certain embodiments, a suitable nitrogen reactant can comprise a nitrogen atom.

In certain embodiments, a suitable boron reactant can comprise a boron compound having at least one organic ligand. In certain embodiments, the organic ligand can have a double bond and/or a triple bond. In certain embodiments, the organic ligand can be a ring ligand. In certain embodiments, the organic ligand may comprise a delocalized electron. In certain embodiments, a suitable boron reactant can comprise a trialkyl boron compound. In certain embodiments, a suitable boron reactant can comprise triethylboron (B(C ₂ H ₅ ) ₃ , TEB). In certain embodiments, a suitable reactant may comprise boron trimethyl boron _{(B (CH 3) 3,} TMB). In certain embodiments, suitable boron reactants can comprise a linear or branched alkyl group (including, for example, a linear or branched C ₃ -C ₈ and more preferably a linear or branched C ₃ -C ₅ a trialkyl boron compound. Suitable boron reactants can include a variety of other boron-containing reactants. In certain embodiments, the boron reactant can comprise a boron halide, an alkyl boron, and/or a borane. In certain embodiments, the boron reactant can comprise a boron halide, a borane halide, and a complex thereof. For example, a suitable boron halide can have a boron to halide ratio of from about 0.5 to about 1.

Suitable boranes may comprise a compound according to formula I or formula II. B _n H _n+x (Formula I) wherein n is an integer from 1 to 10, preferably from 2 to 6, and x is an even number, preferably 4, 6 or 8. B _n H _m (Chemical Formula II) wherein n is an integer of from 1 to 10, preferably from 2 to 6, and m is an integer of from 1 to 10, preferably from 2 to 6, different from n.

Examples of the above boranes according to Formula I include nest-borane (B _n H _n+4 ), spider-borane (B _n H _n+6 ), and open-chain-borane (B _n H _n+8 ). Examples of the borane according to Chemical Formula II include a fused-borane (B _n H _m ). Further, a borane complex such as (CH ₃ CH ₂ ) ₃ N--BH ₃ can be used.

In certain embodiments, suitable boron reactants can include borane halides, particularly fluorides, bromides, and chlorides. An example of a suitable compound is B ₂ H ₅ Br. Other examples include boron halides having a high boron / halide ratio, such as _{B 2 F 4, B 2 C} l4 and B ₂ Br _4. Halogenated borane complexes can also be used.

In certain embodiments, a halogenoborane according to Formula III can be a suitable boron reactant. B _n X _n (Formula III) wherein X is chlorine (Cl) or bromine (Br), and n is an integer of 4 or 8 to 12 when X is chlorine, or n is an integer of 7 to 10 when X is bromine .

In certain embodiments, the carborane according to Formula IV can be a suitable boron reactant. C ₂ B _n H _n+x (Formula IV)

Examples according to the carborane Formula IV include Closed - carborane _{(C 2 B n H n +} 2), nested - carborane _{(C 2 B n H n +} 4), and the web of formula - C Borane (C ₂ B _n H _n+6 ).

In certain embodiments, the amine-borane adduct according to Formula V can be a suitable boron reactant. R ₃ NBX ₃ (Formula V) wherein R is a straight or branched chain C1 to C10, preferably a C1 to C4 alkyl group or H, and X is a linear or branched C1 to C10, preferably a C1 to C4 alkane. Base, H or halogen.

In certain embodiments, the amine borane according to Formula VI wherein one or more of the substituents on the boron are amine groups can be a suitable boron reactant. R ₂ N (Formula VI) wherein R is a linear or branched C1 to C10, preferably a C1 to C4 alkyl group or a substituted or unsubstituted aryl group.

An example of a suitable amine borane is (CH ₃ ) ₂ NB(CH ₃ ) ₂ .

In certain embodiments, a suitable boron reactant can comprise a cyclazepine (--BH--NH--) ₃ and/or a volatile derivative thereof.

In certain embodiments, the alkyl boron or alkyl borane can be a suitable boron reactant wherein the alkyl group is typically a linear or branched C1 to C10 alkyl group, preferably a C2 to C4 alkyl group.

In certain embodiments, it may be desirable to load a substrate (eg, a semiconductor workpiece) on which a tantalum nitride film comprising boron and carbon is deposited into a reactor chamber. The reactor chamber can be part of a clustering tool in which various processes in the formation of integrated circuits are performed. In certain embodiments, it may be in a batch processing reactor (including, for example, in a mini batch reactor (eg, a reactor having a capacity of 8 substrates or less than 8 substrates) and/or batching in a furnace Processing the reactor (eg, a reactor having a capacity of 50 or more than 50 substrates) performs one or more deposition processes described herein. In certain embodiments, one or more of the deposition processes described herein can be performed in a single wafer reactor. In certain embodiments, a space reactor chamber (eg, a space ALD reactor chamber) may be suitable. In certain embodiments, a reactor chamber having a cross-flow configuration may be suitable. In certain embodiments, a reactor chamber having a spray head configuration may be suitable.

An exemplary single wafer reactor is commercially available under the tradenames Pulsar® 2000 and Pulsar® 3000 from ASM USA of Fenix, Arizona, and ASM, commercially available under the trade names Eagle® XP and Eagle® XP8 from Tokyo, Japan. Japan Corporation. An exemplary batch processing ALD reactor is commercially available under the trade designations A400 ^(TM) and A412 ^(TM) from ASM Europe Ltd. of Almere, The Netherlands.

14 is a flow chart showing another example of a process 800 for forming a tantalum nitride film (eg, a SiN (B, C) film) comprising boron and a carbon component. Process 800 can include a sequencing 802 having a process 804 for forming tantalum nitride on the surface of the substrate and a process 812 for introducing boron and carbon components into the tantalum nitride. In some embodiments, the ordering 802 can be repeated multiple times to form a SiN (B, C) film having the desired composition and/or thickness. The ratio of the number of times process 804 is performed to the number of times process 812 is performed may be varied to fine tune the concentration of boron and carbon components in the film and thus to achieve a film having the desired characteristics. For example, the ratio of the number of times process 804 is repeated to the number of times process 812 is repeated can be selected to provide a film having the desired boron and carbon component content.

Process 804 for forming tantalum nitride on the surface of the substrate can include blocks 806, 808, and 810. In block 806, the substrate can be exposed to one or more ruthenium reactants. In block 808, the substrate can be exposed to one or more nitrogen reactants. In block 810, blocks 806 and 808 may be repeated multiple times (e.g., the number of cycles of process 804). In certain embodiments, exposing the substrate to the one or more ruthenium reactants in block 806 can include exposing the substrate to a ruthenium reactant pulse and exposing the substrate to the one or more nitrogen reactions in block 808 The article can include exposing the substrate to a nitrogen reactant pulse. In certain embodiments, the ruthenium reactant pulse of block 806 and the nitrogen reactant pulse of block 808 are by a purge step to remove excess ruthenium reactants and/or reaction by-products from the reactor chamber (Fig. Separated by not shown). The purging step can include flowing the purge gas and/or evacuating the reactor chamber (eg, by evacuating the reactor chamber) to remove or substantially remove excess reactants and/or reaction pairs. product. In some embodiments, the purging step (not shown) is performed, for example, by exposing the substrate to the one or more nitrogen reactants in block 808, prior to performing the repetitive process in block 810. Excess nitrogen reactants and/or reaction by-products are removed. In some embodiments, process 804 is an ALD process. In certain embodiments, process 804 is a CVD process in which one or more of the reactants are at least partially decomposed on the surface of the substrate. In certain embodiments, the pulse of the ruthenium reactant and the pulse of the nitrogen reactant may at least partially overlap.

Process 812 for introducing boron and carbon components into tantalum nitride can include blocks 814 and 816. In block 814, the substrate can be exposed to one or more boron reactants. In block 816, block 814 may be repeated multiple times (e.g., the number of cycles of process 812). In certain embodiments, exposing the substrate to the one or more boron reactants comprises exposing the substrate to a boron reactant pulse. For example, in block 816, the boron reactant pulse of block 814 can be repeated multiple times. In certain embodiments, each boron reactant pulse can be separated by a purge step (not shown) to remove excess boron reactants and/or reaction byproducts. In some embodiments, a single boron reactant pulse is provided (eg, no repetition of process 814 is performed). In certain embodiments, the one or more boron reactants are provided under CVD conditions to decompose the one or more boron reactants on a surface of the substrate.

In some embodiments, the process for forming a SiN (B, C) film (eg, process 800 shown in FIG. 14) can be a hybrid process including both an ALD process and a CVD process. For example, a process for forming a tantalum nitride (SiN) film (eg, process 804 of FIG. 14) can include an ALD process and is used to direct boron and carbon components to a tantalum nitride (SiN) film. The process (eg, process 812 shown in FIG. 14 to form a SiN (B, C) film) can include a CVD process.

In certain embodiments, no plasma is used in any of 804 or 812. For example, process 804 and/or process 812 can include a thermal process, such as a thermal ALD process and/or a thermal CVD process.

Silicon reactant ALD process for providing a silicon nitride film (SiN) may comprise octachlorotrisilane Silane _{(Si 3 Cl 8, octachlorotrisilane,} OCTS) and / or hexachlorodisilane Silane _{(Si 2 Cl 6, hexachlorodisilane,} HCDS) And the nitrogen reactant of the ALD process may comprise ammonia (NH ₃ ). Exposing the substrate to silicon reactant (e.g., block 806 shown in FIG. 14) may include exposing the substrate to a Si ₃ Cl ₈ and / or Si ₂ Cl _6. By way of example, Si ₃ Cl ₈ and/or Si ₂ Cl _{6 can be} fed to the reactor chamber (eg, helium reactant pulse) for a certain duration, for example by means of a nitrogen carrier gas. Exposing the substrate to a nitrogen reactant (e.g., a block 808 shown in FIG. 14) may include exposing the substrate to NH _3. By way of example, NH ₃ can be fed to a reactor chamber (eg, a nitrogen reactant pulse) for a certain duration, for example by means of a nitrogen carrier gas. The pulse length of the ruthenium reactant pulse and/or nitrogen reactant pulse can range from about 0.05 seconds to about 5.0 seconds, from about 0.1 second to about 3 seconds, or from about 0.2 seconds to about 1.0 second. For example, the nitrogen reactant pulse and/or the ruthenium reactant pulse can be about 1 second.

As described herein, a purge step can be performed in the ALD process after the reactants are used to deliver one or more reactants to the reactor chamber, for example to remove excess reactants from the vicinity of the substrate surface and/or Reaction by-product. Gases such as nitrogen (N ₂ ), argon (Ar), and/or helium (He) can be used as a purge gas to help remove excess reactants and/or reaction by-products. In certain embodiments, the ALD process purge step can be from about 1 second to about 20 seconds, from about 1 second to about 15 seconds, or from about 1 second to about 10 seconds, including about 5 seconds. For example, one cycle of an ALD process for exposing a substrate to a ruthenium reactant and/or a nitrogen reactant can include a reactant pulse of about 0.5 seconds followed by a purge step of about 5 seconds. In certain embodiments, one cycle of the ALD process can include a helium reactant pulse of about 0.5 seconds, followed by a purge step of about 5 seconds, followed by a nitrogen reactant pulse of about 0.5 seconds, and then about 5 later. Second wash step.

The cycle of the ALD process can be repeated multiple times until a film having the desired thickness and/or composition is obtained. In certain embodiments, deposition parameters such as reactant flow rate, reactant flow duration, purge step duration, and/or reactants themselves may vary during one or more deposition cycles during the ALD process, A film having the desired characteristics is obtained. For example, one or more deposition parameters of an ALD process cycle can be different than one or more deposition parameters of another ALD process cycle.

As described herein, in certain embodiments, a process for depositing a tantalum nitride film (eg, a SiN (B, C) film) comprising boron and a carbon component can include a chemical vapor deposition (CVD) process. The CVD process for introducing boron and carbon components into the tantalum nitride film can include decomposition of one or more reactants on the tantalum nitride film and/or chemical interactions between the plurality of reactants. For example, the reactants can be fed into a reactor chamber, the decomposition of which facilitates the formation of the desired membrane. In certain embodiments, a suitable boron reactant can comprise triethylboron (B(C ₂ H ₅ ) ₃ , TEB) and/or trimethylboron (B(CH ₃ ) ₃ , TMB). For example, the TEB fed into the reactor chamber can be decomposed on the tantalum nitride film to facilitate the introduction of boron and carbon components into the tantalum nitride film.

In some embodiments, a pulsed CVD process can be used. In some embodiments, the process for depositing a SiN (B, C) film includes an ALD process for providing a tantalum nitride SiN film on a surface of the substrate, and a CVD process performed after at least one cycle of the ALD process, The CVD process is used to direct boron and carbon components into a tantalum nitride film to form a SiN (B, C) film (eg, pulses for delivering pulses of one or more boron reactants into the reactor chamber) CVD process). In some embodiments, the CVD process can be repeated multiple times to provide a SiN (B, C) film having the desired composition (eg, a CVD process that will include a reactant pulse and a subsequent CVD process). Overlay). In certain embodiments, the CVD process for introducing boron and carbon components is not a pulsed CVD process such that boron reactants are fed into the reactor chamber in a continuous stream or substantially continuous stream to achieve the desired boron. And a SiN (B, C) film having a carbon component content.

The pulsed CVD process can include feeding a reactant gas (eg, a reactant pulse) into the reactor chamber for a certain duration. In certain embodiments, the reactant pulse of the CVD process can have a duration of from about 0.05 seconds to about 5.0 seconds, from about 0.1 seconds to about 3 seconds, or from about 0.2 seconds to about 1.0 seconds. For example, the reactant pulse can be about 0.5 seconds.

In certain embodiments, the spacing between the two reactant pulses can include the flow of the one or more reactants that interrupt the reactant pulse. The interval between reactant pulses can have a duration of from 1 second to about 20 seconds, including from about 1 second to about 15 seconds, or from about 1 second to about 10 seconds. For example, the interval can be about 5 seconds. In certain embodiments, the spacing includes transporting the substrate to a non-reactive or substantially non-reactive space. In certain embodiments, the interval comprises a purge step. For example, the spacing can include the step of transporting the substrate to a space free of reactants or substantially non-reactive and a purge step. For example, the purging step can be performed after the pulse for delivering one or more reactants to the reactor chamber for the pulsed CVD process, for example to remove excess reactants from the vicinity of the surface of the substrate and/or Reaction by-product. The purge step can include flowing one or more inert gases (eg, argon (Ar), helium (He), and/or nitrogen (N ₂ ) through the reactor chamber. In some embodiments, each can be A reactant pulse is followed by a purge step. The purge step can include removing excess reactants and/or by-products from the vicinity of the substrate. In some embodiments, the CVD process purge step can have from about 1 second to about A duration of 20 seconds, from about 1 second to about 15 seconds, or from about 1 second to about 10 seconds. For example, the purge process can be about 5 seconds. Other durations of the reactant pulse and/or purge process are also It may be suitable, as determined by those skilled in the art, depending on the particular circumstances.

Wherein the suitable duration of the reactant gas supply to the reactor chamber and/or the duration of the purge step, the reactant pulse and/or the gas flow rate in the purge step may be dependent on one or more of the reaction processes Parameters such as adjusting reactant pulse duration and/or reactant pulse gas flow rate, and/or purge step duration and/or purge step gas flow rate to provide desired reactants to the surface of the substrate and/or Or remove the desired reactants from the vicinity of the substrate surface.

As described herein, the process for depositing a SiN (B, C) film can include multiple repetitions of a process for providing a tantalum nitride film, and subsequent introduction of boron and carbon components to the nitride. Multiple iterations of the process in the diaphragm (eg, sort 802 shown in Figure 14). In some embodiments, the ordering can be repeated multiple times (eg, the ordering is repeated Z times) to provide a SiN(B,C) film having the desired composition and/or thickness. For example, a process for forming a SiN (B, C) film can include multiple cycles of an ALD process for depositing a tantalum nitride SiN film, and subsequent introduction of boron and carbon components to the nitride. The sequencing of the plurality of cycles of the CVD process in the 矽SiN film is repeated a plurality of times to provide a SiN(B,C) film having the desired composition and/or thickness.

In some embodiments, multiple cycles of an ALD process including deposition of a tantalum nitride film and subsequent cycles of introducing a boron and carbon component into a CVD process in a tantalum nitride film may be employed. The ordering is repeated from about 1 to about 150, including from about 25 to about 75. For example, the ranking can be repeated about 75 times. For example, the ranking can be repeated 100 times.

Multiple cycles of the process for providing a tantalum nitride (SiN) film in the sorting (eg, X cycles of the ALD process, such as repeating the process 804 shown in FIG. 14 multiple times or performing multiple cycles) and/or Or a plurality of cycles of a process for introducing boron and carbon components into tantalum nitride (eg, Y cycles of a CVD process, such as repeating process 812 shown in FIG. 14 multiple times or performing multiple cycles), To achieve the desired film properties. For example, the ordering can include multiple cycles of the ALD process followed by multiple cycles of the CVD process. The number of ALD cycles and/or the number of CVD cycles can be varied to provide a SiN(B,C) film comprising the desired composition and/or thickness. For example, the number of cycles of the process for introducing boron and carbon components can be selected to provide a SiN (B, C) film having the desired boron and carbon component content (eg, to exhibit the desired etch rate). , conformal efficacy, and / or other film properties).

In certain embodiments, the number of cycles of the process for providing the boron and carbon components of the tantalum nitride film within the sequencing may range from about 1 cycle to about 20 cycles, including from about 1 cycle to about 10 cycles. In certain embodiments, the process for providing boron and carbon components can be repeated five times. For example, a pulsed CVD process for introducing boron and carbon components into a tantalum nitride film can be repeated three times within the ordering. The cycle for providing the boron and carbon components can be performed prior to additional cycles of the process for depositing the tantalum nitride SiN film. For example, the ordering of the SiN (B, C) film deposition process may include: first, a process cycle for depositing a tantalum nitride SiN film, and secondly, a process cycle for adding boron and a carbon component to the SiN film. repeatedly.

In some embodiments, the ratio of the number of cycles of the process for depositing the tantalum nitride film to the number of cycles for introducing the boron and carbon components (eg, the ratio of Y:X) may be about 1 : 1 to about 100:1, including about 3:1 to about 50:1. In some embodiments, the ratio of the number of cycles of the process of depositing the tantalum nitride film within the process to the number of cycles used to introduce the boron and carbon components can range from about 5:1 to about 20:1. The ratio can be expressed as a percentage or a boron carbon process fraction, such as a percentage of the total number of cycles in the ordering of the process for introducing boron and carbon components. For example, the percentage of the total number of cycles in the order of the boron carbon process or in the ordering process for introducing boron and carbon components can be adjusted to provide a SiN (B, C) film having the desired composition. The percentage or boron carbon process score can be calculated by the following equation: X / (X + Y) * 100%. In certain embodiments, the percentage of the total number of cycles of the boron carbon process fraction or the ordering process for introducing boron and carbon components may range from about 0.01% to about 50%, including from about 5% to about 20%. . For example, the boron carbon process score can be about 10%. For example, a process having a boron carbon process fraction of from about 5.0% to about 10% can form a SiN _x (B _y , C _z ) film, where x can range from about 1.3 to about 1.8 and y can range from about 0.5 to about 1.5. And z can be from about 0.3 to about 1.3.

The first stage and/or the second stage of the ALD process and/or CVD process can be performed at a process temperature of from about 25 ° C to about 800 ° C, including from about 100 ° C to about 600 ° C. Process temperatures as referred to herein may include the reactor chamber susceptor, the temperature of the reactor chamber walls, and/or the temperature of the substrate itself. In certain embodiments, the first stage and/or the second stage of the ALD process and/or CVD process can be performed at a process temperature of from about 150 °C to about 500 °C. For example, one or both of the first and second stages of the ALD process and/or CVD process can be performed at a process temperature of from about 200 °C to about 400 °C. For example, the methods described herein can be performed in a reactor chamber having a susceptor, substrate, and/or reactor chamber wall and heated to a temperature of from about 200 ° C to about 400 ° C (eg, a temperature of about 400 ° C) The first phase and/or the second phase of one or more cycles of the ALD process. For example, the CVD process can be performed in a reactor chamber having a susceptor, substrate, and/or reactor chamber wall and heated to a temperature of about 400 °C. In certain embodiments, the boron and carbon components can be introduced into the tantalum nitride at a process temperature of less than 400 ° C (including, for example, from about 325 ° C to about 400 ° C and from about 350 ° C to about 400 ° C). CVD process.

In certain embodiments, the process for depositing a tantalum nitride SiN film and/or the process for introducing boron and carbon components can be sufficiently high to provide a process with reduced thermal budget while facilitating Decomposition of one or more reactants (eg, ruthenium reactants and/or nitrogen reactants of the ALD process, and/or boron reactants of the CVD process), and/or between reactants and/or reactants and substrate surfaces The reaction between the two. In certain embodiments, the process temperature for depositing the tantalum nitride SiN film and/or introducing boron and carbon components can range from about 325 ° C to about 800 ° C, including from about 350 ° C to about 600 ° C to about 400 ° C. About 600 ° C, or about 375 ° C to about 450 ° C. For example, a CVD process for introducing boron and carbon components into tantalum nitride can be performed at a process temperature of about 400 ° C (eg, including decomposing the boron reactant TEB to direct boron and carbon components to CVD process of tantalum nitride film). In certain embodiments, an ALD process for depositing a tantalum nitride (SiN) film can be performed at a process temperature of about 400 ° C (eg, an ALD process in which one or more reactants can decompose when forming a SiN film) . In some embodiments, the temperature of the ALD process can be different than the temperature of the CVD process. In some embodiments, the same temperature is used for the ALD process for forming a tantalum nitride SiN film and the CVD process for adding boron and carbon components to the SiN film.

A thermal ALD process for forming a tantalum nitride SiN film (for example, in a Pulsar® 3000 chamber commercially available from ASM USA of Fenix, Arizona) for forming SiN (B, C) An example of a deposition process for a film. The thermal ALD process can be performed on a 300 millimeter (mm) wafer at a process temperature of about 400 ° C, the wafer containing octachlorotrioxane (Si) fed to the reactor chamber with a carrier gas (eg, nitrogen) ₃ Cl _{8, octachlorotrisilane,} OCTS) silicon reactant, such that the silicon reactant pulse having a duration of about one second and then purged process has a duration of about 5 seconds (e.g., containing blowing nitrogen purge gas) . The OCTS can be stored in a bubbler at a temperature of about 40 ° C and supplied to the reactor chamber from the bubbler (eg, can be kept open by controlling a valve for delivering OCTS to the reactor chamber) The degree to control the mass flow rate of OCTS). Thermal ALD process may comprise containing ammonia (NH ₃₎ is fed to the reactor chamber in a nitrogen reactant, such that the nitrogen reactant pulses have a duration of about one second and is performed after the nitrogen reactant pulse has about 5 seconds The duration of the purge process (for example, using a purge gas containing nitrogen). May be maintained at a pressure from about 1.5 bar to provide a gas source to the reactor chamber NH ₃ (e.g., can be used by controlling the NH ₃ delivered to the reactor chamber holding a valve opening degree controlled NH ₃ Mass flow rate). The ALD process can be cycled multiple times. Multiple cycles of the thermal CVD process for introducing boron and carbon components into the SiN film can be performed after multiple cycles of the ALD process. The thermal CVD process can be performed at a temperature of about 400 ° C and can include a boron reactant for providing a boron reactant comprising triethylboron (B(C ₂ H ₅ ) ₃ , TEB) to the reactor chamber. A pulse, wherein the boron reactant pulse can have a duration of about 0.5 seconds. A purge step having a duration of about 5 seconds (e.g., using a purge gas comprising nitrogen) can be performed after the boron reactant pulse. For example, the SiN (B, C) deposition process can include a 9 cycle including an ALD process and a 2 cycle ordering of the subsequent CVD process (eg, providing about 10% boron carbon process score), wherein the ordering It was repeated 75 times.

The composition of the film can be adjusted, for example, by increasing or decreasing the boron carbon process fraction for the process of depositing a tantalum nitride film comprising boron and carbon components. For example, the boron and carbon content of the film can be adjusted by adjusting the boron carbon process fraction of the film fabrication process. In certain embodiments, the tantalum nitride film comprising boron and carbon components can have from about 0.1 atomic percent to about 50 atomic percent boron, including from about 1 atomic percent to about 35 atomic percent boron. For example, a tantalum nitride film comprising boron and a carbon component can have from about 5 atomic percent to about 30 atomic percent boron. In certain embodiments, the tantalum nitride film comprising boron and a carbon component can have from about 0.1 atomic percent to about 50 atomic percent carbon, including from about 1 atomic percent to about 35 atomic percent carbon. For example, a tantalum nitride film comprising boron and a carbon component can have from about 5 atomic percent to about 30 atomic percent carbon. In some embodiments, the enthalpy and/or nitrogen content can be adjusted by adjusting the boron carbon process fraction of the film making process.

In certain embodiments, a SiN(B,C) film formed in accordance with one or more processes described herein can have a desired dielectric constant (kappa-value). The dielectric constant of the SiN (B, C) film can be lower than that of the conventional tantalum nitride film. In certain embodiments, the SiN (B, C) film can have a dielectric constant of less than about 7, including less than about 6. For example, a SiN(B,C) film can have a dielectric constant between about 4.8 and about 7, including between about 4.8 and 6, and between about 4.8 and about 5.5. In some embodiments, the dielectric constant of the film can be adjusted by adjusting the boron carbon process of the SiN (B, C) film fabrication process. In certain embodiments, a SiN(B,C) film having a dielectric constant of about 5.5 can be formed using a deposition process having a boron carbon process fraction of about 10% or greater. Certain applications for semiconductor devices (eg, spacer materials that are characteristic of transistor gates) have a reduced dielectric constant (eg, a dielectric constant that is less than the dielectric constant of a conventional tantalum nitride film). The SiN (B, C) film can be beneficial for improving one or more device electrical parameters, including device parasitic capacitance reduction.

As described herein, the SiN (B, C) film can be a sacrificial film in a semiconductor device fabrication process. For example, a SiN (B, C) film can be selectively removed during the etching process. In some embodiments, the sacrificial SiN (B, C) film can be fabricated in a semiconductor device using an etching process including chlorine (Cl) and/or fluorine (F) (eg, a plasma process containing chlorine and/or fluorine). It is selectively removed during the period. In some embodiments, a SiN (B, C) film can form part of a fabricated semiconductor device. For example, a SiN (B, C) film can be more resistant to etching than one or more other materials used in the fabrication of semiconductor devices.

The SiN (B, C) film can have the desired etch selectivity to another material in the device. For example, the etch selectivity of the film can be fine tuned by adjusting the boron and carbon component content of the SiN (B, C) film (eg, by adjusting the boron carbon process fraction of the film fabrication process). In some embodiments, the SiN (B, C) film can be etched by a dry etch process and/or a wet etch process. For example, a SiN (B, C) film can be etched by a plasma etching process including a fluorine-containing plasma. In certain embodiments, the SiN (B, C) film can have an etch selectivity (eg, dry etch and/or wet etch selectivity) of about 5 or greater than another material of the device, including about 10 Or a selectivity greater than 10, about 20 or greater than 20, or about 50 or greater than 50.

In certain embodiments, the SiN (B, C) film can exhibit the desired wet etch selectivity, such as wet etch selectivity to a hot yttrium oxide (TOX) layer. For example, a SiN (B, C) film can be more resistant to wet etching than a hot ruthenium oxide layer such that the ratio of the wet etch rate of the SiN (B, C) film to the wet etch rate of the thermal yttrium oxide layer is less than About 1, less than about 0.5, or less than about 0.3. In certain embodiments, the ratio of the wet etch rate of the SiN (B, C) film to the wet etch rate of the thermal yttrium oxide layer can be less than about 0.1.

In certain embodiments, one or more tantalum nitride films (SiN(B, C)) comprising boron and a carbon component formed according to one or more processes described herein can have a plurality of etching solutions The required etch rate. In certain embodiments, a tantalum nitride film (eg, a SiN (B, C) film) comprising boron and a carbon component can withstand or substantially withstand one or more wet etchants. For example, the SiN (B, C) film can have less than about 1 nanometer per minute (nm/min) in one or more of the following etching solutions at the provided temperature (including less than about 0.5 nm/ An etch rate of minutes, including less than about 0.2 nanometers per minute, and including less than about 0.1 nanometers per minute: a solution of nitric acid (HNO ₃ ) concentrated at about 80 ° C (eg, having from about 65% to about 75 weights) % solution of HNO ₃ concentration), 5.5% by weight of hydrofluoric acid (HF) at room temperature (for example, a temperature of about 25 ° C), nitric acid at a temperature of about room temperature (for example, a temperature of about 25 ° C): hydrogen A solution of hydrofluoric acid:water (HNO ₃ :HF:H ₂ O) having a ratio of about 1:1:5, having about 10% by weight of sodium hydroxide at about room temperature (for example, a temperature of about 25 ° C) a NaOH aqueous solution of NaOH) concentration, a hydrochloric acid (HCl) solution concentrated at about room temperature (for example, a temperature of about 25 ° C) (for example, a solution having a HCl concentration of about 35% by weight to about 40% by weight), and concentrated sulfuric acid solution at about room temperature (e.g., to a temperature of about 25 deg.] C) (H ₂ SO ₄₎ (e.g., a solution having a concentration of ₄ H ₂ SO greater than about 90% by weight)

In certain embodiments, a tantalum nitride film (eg, a SiN (B, C) film) comprising boron and a carbon component can be tolerated or substantially tolerated at about room temperature (eg, a temperature of about 25 ° C) A wet etchant comprising phosphoric acid (H ₃ PO ₄ ) at a concentration of about 85% by weight. In certain embodiments, a tantalum nitride film (eg, a SiN (B, C) film) comprising boron and a carbon component can withstand or substantially withstand one or more of the following wet etchants (eg, , an etch rate of less than about 3 nanometers per minute (nm/min), and immersed in 1% by weight of hydrofluoric acid (HF) for about 2 minutes): at about room temperature (eg, a temperature of about 25 ° C) Phosphoric acid (H ₃ PO ₄ ) at a concentration of about 85% by weight, an aqueous solution of sodium hydroxide (NaOH) having a concentration of about 10% by weight at about room temperature (for example, a temperature of about 25 ° C), at about room temperature (for example, a temperature of about 25 ° C) a hydrochloric acid (HCl) solution having a concentration of about 35% by weight to about 40% by weight (for example, about 37% by weight), and at about room temperature (for example, a temperature of about 25 ° C) A solution of sulfuric acid (H ₂ SO ₄ ) having a concentration greater than about 90% by weight (eg, 98% by weight).

In certain embodiments, the SiN (B, C) film may have a ratio of hydrogen peroxide: hydrofluoric acid: water (H ₂ O ₂ : HF : H ₂ O) by volume of about 5:5:90. The solution has an etch rate of greater than about 1.0 nanometers per minute (nm/min) at about room temperature (e.g., at a temperature of about 25 °C). In certain embodiments, the SiN (B, C) film can be in an oxygen-containing environment (including, for example, ozone and/or an oxygen-containing plasma (eg, a plasma containing oxygen atoms and/or other oxygen-containing free radicals) In)) etching is performed after being exposed to the treating agent.

As described herein, a SiN (B, C) film can be deposited on and/or over a three-dimensional (3-D) structure while exhibiting the desired conformality or step coverage. In certain embodiments, the SiN(B,C) film can have a ratio of about 2:1 or greater than 2:1 (including about 3:1 or greater than 3:1, about 5:1, or greater than 5:1). Or a three-dimensional structure of an aspect ratio of about 8:1 or higher than 8:1) exhibits the desired conformality or step coverage. In certain embodiments, the SiN(B,C) film can have a ratio of about 10:1 or greater than 10:1, about 25:1, or greater than 25:1, or about 50:1 or greater than 50:1. The three-dimensional structure of the aspect ratio exhibits the desired conformality or step coverage. In certain embodiments, a SiN (B, C) film can exhibit a desired step coverage on one or more features as described herein, including about 80% or greater than 80% (including about 90% or Step coverage above 90%, about 95% or above 95%, or about 100%). In certain embodiments, the SiN (B, C) film can be exhibited when formed on a three-dimensional structure having an aspect ratio of up to about 250:1 (including up to about 150:1 and up to about 100:1) Step coverage of about 80% or greater than 80% (including about 90% or greater than 90%, about 95% or greater than 95%, or about 100%).

In some embodiments, a portion of the SiN (B, C) film deposited on the sidewalls of the three-dimensional structure can exhibit the desired etch rate compared to a portion of the film deposited on the top surface of the three-dimensional feature. Etching rate. In certain embodiments, a portion of the SiN (B, C) film deposited on the sidewalls of the three-dimensional structure may exhibit a portion of SiN (such as a SiN (B, C) film deposited on the top surface of the structure ( B, C) Uniform or substantially uniform etch rate of the film. For example, the ratio of the etch rate of the sidewall portion of the SiN (B, C) film to the etch rate of the top portion of the SiN (B, C) film can be less than about 4, including less than about 2, about 1.5. In certain embodiments, the ratio is about 1.

In certain embodiments, a tantalum nitride film (eg, a SiN (B, C) film) comprising boron and a carbon component can be subjected to an annealing process after it is formed. In certain embodiments, the SiN (B, C) film can be annealed in an inert gas environment (eg, an environment comprising nitrogen and/or one or more inert gases). For example, the annealing process can be performed at a temperature of about 600 ° C or higher, about 800 ° C or higher, or 1000 ° C or higher than 1000 ° C in a nitrogen atmosphere. In certain embodiments, the SiN (B, C) film can be annealed at temperatures up to about 900 °C. In certain embodiments, the SiN (B, C) film can be at a temperature of, for example, about 600 ° C or higher, about 800 ° C or higher, or 1000 ° C or higher than 1000 ° C in a hydrogen atmosphere ( Annealing is carried out including up to about 900 ° C). In certain embodiments, the boron and carbon components of the SiN (B, C) film do not diffuse out of the film when annealed at temperatures up to about 900 ° C in a nitrogen atmosphere. In certain embodiments, the annealing can be performed in a hydrogen or inert gas environment, such as at a temperature of about 600 ° C or above, about 800 ° C or above, or 1000 ° C or above 1000 ° C.

An example of a SiN (B, C) film

Figure 15A graphically illustrates a boron carbide process fraction having from about 0% to about 15% (e.g., a cycle for introducing boron and carbon content into a tantalum nitride SiN film as a percentage of the total number of cycles) The composition of the four membranes (for example, as measured by rutherford backscattering spectrometry (RBS)). The atomic percentages of cerium, nitrogen, boron, carbon, and chlorine are shown for each of the four films, wherein the atomic percentages of cerium, nitrogen, boron, and carbon are shown with reference to the left vertical axis, and the atomic percentage of chlorine refers to the right vertical The axis is shown. Each of the four films can be formed according to one or more processes as described herein. For example, SiN films and SiN (B, C) films with varying compositions can be utilized in depositions performed in Pulsar® 3000 chambers (eg, ASM USA, commercially available from Fenix, Arizona). The process is deposited using a thermal ALD process for forming a tantalum nitride SiN film. The thermal ALD process can be performed on a 300 millimeter (mm) wafer at a temperature of about 400 ° C and at a pressure of about 0.1 Torr to about 10 Torr, the wafer containing the feed with a carrier gas (eg, nitrogen) The ruthenium reactant of octachlorotrioxane (Si ₃ Cl ₈ , OCTS) in the reactor chamber is such that the ruthenium reactant pulse has a duration of about 1 second and then a purge step having a duration of about 5 seconds is performed ( For example, a purge gas containing nitrogen is used. The OCTS can be stored in a bubbler at a temperature of about 40 ° C and supplied to the reactor chamber from the bubbler (eg, can be kept open by controlling a valve for delivering OCTS to the reactor chamber) The degree of control of the mass flow rate of OCTS). Thermal ALD processes may contain contain is fed to an ammonia (NH ₃₎ reactor chamber nitrogen reactant, such that the nitrogen reactant pulses have a duration of about one second and is performed after the reactant pulses have about 5 seconds A duration purge step (eg, using a purge gas containing nitrogen). May be maintained at a pressure from about 1.5 bar to provide a gas source to the reactor chamber NH ₃ (e.g., can be used by controlling the NH ₃ delivered to the reactor chamber holding a valve opening degree controlled NH ₃ Mass flow rate). The ALD process can be cycled multiple times. Multiple cycles of the pulsed thermal CVD process for introducing boron and carbon components into the SiN film can be performed after multiple cycles of the ALD process. The thermal CVD process can be performed at a temperature of about 400 ° C and a pressure of about 0.1 Torr to about 10 Torr, and can comprise triethylboron (B(C ₂ H ₅ ) ₃ , TEB) fed into the reactor chamber. Boron reactant, wherein the boron reactant pulse can have a duration of about 0.5 seconds, followed by a purge step having a duration of about 5 seconds after the reactant pulse (eg, using a purge gas comprising nitrogen) . For example, the SiN (B, C) deposition process can include a plurality of cycles including an ALD process and a sequence of one to three cycles of the subsequent CVD process (eg, to provide about 0% to about 15% of the boron carbon process) Score), wherein the ordering can be repeated multiple times (eg, about 50 times to about 100 times). For example, the ordering can be repeated 75 times.

The graph shown in Figure 15A shows that the boron and carbon content of the film can increase as the boron carbon process fraction increases. For example, the boron and carbon component content may increase linearly or substantially linearly as the boron carbon process fraction increases. Figure 15A shows that the niobium content and the nitrogen content may decrease as the boron carbon process fraction increases. For example, the enthalpy and/or nitrogen content may decrease linearly or substantially linearly as the boron carbon process fraction increases. Figure 15A further shows that the chlorine content can decrease as the boron carbon process fraction increases.

Figure 15B graphically illustrates the film growth rate in angstroms per cycle (Å/cycle) of four films formed by a fabrication process having a boron carbon process fraction of from about 0% to about 15%. The cycle as shown in FIG. 15B may correspond to a plurality of cycles including a process for providing a tantalum nitride (SiN) film, and a plurality of cycles for introducing boron and carbon into a process in the SiN film. (For example, sort 802 shown in Figure 14). Each of the four films can be formed according to one or more processes as described herein (eg, as described with reference to Figure 15A). Figure 15B shows that the film growth rate can decrease as the boron carbon process fraction increases. Without being bound by any particular theory or mode of operation, the boron reactant adsorbed onto the surface of the substrate can reduce ruthenium reactants and/or nitrogen reactants (eg, ruthenium reactants from subsequent tantalum nitride deposition processes and/or The ability of the nitrogen reactant to properly adsorb onto the surface of the substrate. Increasing the boron carbon process fraction (eg, when providing an increased amount of boron reactant in the SiN (B, C) film fabrication process) can increasingly reduce the ruthenium and/or nitrogen reactants from subsequent tantalum nitride deposition processes. The ability to adsorb onto the surface of the substrate. Moreover, without being limited by any particular theory or mode of operation, the reduced adsorption of germanium and/or nitrogen reactants from subsequent tantalum nitride deposition processes onto the surface of the substrate may also result from a boron carbide process fraction. A film of higher boron and carbon component content that was originally desired.

In certain embodiments, film thickness non-uniformity (eg, 1 sigma (1σ) thickness non-uniformity) may not be adversely affected by the increased boron carbon process score. In certain embodiments, the film thickness non-uniformity remains the same or substantially the same as the increased boron carbon process score. For example, the film thickness non-uniformity of the process for depositing a tantalum nitride film having boron and carbon components can be less than about 20%, including less than about 10% and about 5%. In certain embodiments, film thickness non-uniformity may be improved as the boron carbon process fraction is reduced to a particular value. For example, a boron carbon process fraction of less than about 10% can provide improved film thickness non-uniformity.

Referring to Figure 16, Fourier Transform Infrared Spectroscopy (FTIR) analysis of four films having a boron carbon process fraction of from about 0% to about 15% is shown. Each of the four films can be formed according to one or more processes as described herein (eg, as described with reference to Figure 15A). FTIR indicates the presence of various features within each film, including, for example, the presence of various chemical bonds. For example, FTIR analysis can show changes in the addition and/or characteristics of features of the film after it has been subjected to a film fabrication process. The peak corresponding to each feature of each film in Fig. 16 is labeled "O" or "*" to indicate the origin of the marked feature. For example, a peak labeled "O" in the graph indicates various features (eg, hydrogen (NH) bonded to nitrogen, hydrogen (OH) bonded to oxygen, hydrogen bonded to helium (Si) -H), nitrogen (Si-N) bonded to ruthenium is contributed by the process used to deposit the tantalum nitride SiN film. For example, a peak labeled "*" indicates various features (eg, hydrogen bonded to carbon, hydrogen bonded to boron, carbon bonded to boron, carbon bonded to another carbon, bonded) Boron to another boron is contributed by a process for introducing boron and carbon components into the tantalum nitride SiN film. Figure 16 illustrates that the process for introducing boron and carbon into the tantalum nitride film can provide features such as hydrogen (CH) bonded to carbon and/or hydrogen (BH) bonded to boron (e.g., as in Figure 16 is between 2500 cm ^-1 and about 3000 cm ^-1 ) and for example carbon bonded to boron (BC), boron bonded to another boron (BB), and/or bonded to another A carbon-carbon (CC) or the like (for example, as shown in Fig. 16 between 1000 cm ^-1 and about 1500 cm ^-1 (for example, at about 1200 cm ^-1 )). Figure 16 shows that the Si-H bonding characteristics decrease as the boron carbon process fraction increases. The reduction in Si-H bonding characteristics can be beneficial to improve SiN (B, C) film performance, such as improvements in the electrical properties of the film. Figure 16 also shows that the peak corresponding to nitrogen (Si-N) bonded to ruthenium can shift to a higher wave number as the boron carbon process fraction increases, such as a change in bond between 矽 and nitrogen. .

Figure 17 shows an analysis based on X-ray reflectance (XRR) measurements of four films having a boron carbon process fraction of from about 0% to about 15%. The film thickness in nanometers, the film density in grams per cubic centimeter (g/cm ³ ), and the film roughness in nanometers (nm) are shown. Each of the four films can be formed according to one or more processes as described herein (eg, as described with reference to Figure 15A). Figure 17 shows that the film density decreases as the boron carbon process fraction increases and the film roughness increases slightly as the boron carbon process fraction increases.

Figure 18 is a graph showing a corresponding film formed by a process having various boron carbon process fractions in units of nanometers per minute (nm/min) in a diluted HF solution (e.g., 0.5 wt% HF solution). The wet etch rate. The film can be formed according to one or more processes as described herein (e.g., as described with reference to Figure 9A). As shown in FIG. 18, the wet etch rate of a tantalum nitride film (for example, a SiN (B, C) film) containing boron and a carbon component can be significantly reduced as the boron carbon process fraction is increased. Figure 18 shows that a film deposition process having a boron carbon process fraction of greater than about 5% can produce a SiN (B, C) film with a significantly reduced wet etch rate. For example, a SiN (B, C) film having a desired wet etch rate in diluted HF (eg, a SiN (B, C) film suitable for use in partition walls applications) can have greater than about 10 The process of % boron carbon process fraction is formed.

19A to 19D illustrate the wet etching performance of a tantalum nitride film (for example, a SiN (B, C) film) containing boron and a carbon component deposited on the trench structure 1300 of the substrate. The film can be formed according to one or more processes as described herein (e.g., as described with reference to Figure 15A). 19A and 19C illustrate scanning electron microscope (SEM) images of a trench structure 1300 having a film 1302 on one or more surfaces of the trench structure 1300 prior to exposing the film 1302 to a wet etchant. For example, a wet etchant comprising a dilute hydrofluoric acid (HF) solution (eg, a 0.5 wt% HF solution) is used for a period of time (eg, up to about 2 minutes). 19B and 19D illustrate film 1302 after exposure to a wet etchant. 19B and 19D illustrate that film 1302 is unaffected or substantially unaffected by the wet etchant. For example, the ratio of the wet etch rate of film 1302 to the etch rate of the underlying thermal oxide layer (eg, hot ruthenium dioxide, TOX) can be less than about 3:10. 19B and 19D also illustrate a film 1302 that provides conformal coverage to the trench structure 1300 after wet etching, for example, the film 1302 does not delaminate from the underlying trench structure and/or does not exhibit other disadvantages.

20A-20D illustrate a SiN(B,C) film on the surface of a high aspect ratio trench 1400 after exposure to a wet etchant for about 4 minutes (eg, immersion in diluted hydrofluoric acid (HF or dHF) Scanning electron microscope (SEM) image of the solution (eg, after 0.5% by weight of HF solution). The film can be formed according to one or more processes as described herein (e.g., as described with reference to Figure 15A). 20A is a lower magnification image of structure 1400 at 13kx magnification showing the upper portion 1402 of the trench, the intermediate portion 1404 of the trench, and the lower segment 1406 of the trench. Upper portion 1402 is shown at a higher magnification at 250kx magnification in Figure 20B, intermediate segment 1404 is shown at a higher magnification at 250kx magnification in Figure 20C, and lower segment 1406 is in Figure 20D. The middle is shown at a higher magnification at 250k× magnification. As shown in FIGS. 20A-20D, the SiN (B, C) film may exhibit excellent conformality or step coverage to the high aspect ratio trench 1400 after exposure to the wet etchant. For example, FIGS. 20A-20D illustrate having a thickness of about 20 nanometers formed on the upper portion 1402 of the trench structure 1400, a thickness of about 20 nanometers formed on the intermediate section 1404 of the trench structure 1400, and formation. A SiN(B,C) film having a thickness of about 19 nm on the lower portion 1406 of the trench structure 1400 (eg, about 95% or greater than 95% conformality). The ratio of the wet etch rate of the SiN (B, C) film as shown in FIGS. 20A to 20D to the etch rate of the underlying thermal oxide (eg, hot ruthenium dioxide, TOX) may be less than about 1:2. .

21A-21D illustrate a scanning electron microscope of a tantalum nitride film (eg, a SiN (B, C) film) containing boron and carbon on a surface of a high aspect ratio trench 1500 prior to exposure to a wet etchant. (SEM) image. The film can be formed according to one or more processes as described herein (e.g., as described with reference to Figure 15A). 21A is a lower magnification image of the trench structure 1500 at 11k× magnification, and FIG. 21B shows the upper portion 1502 of the trench 1500 at a higher magnification of 200k×, and FIG. 21C at 200k×. The middle section 1504 of the trench 1500 is shown at high magnification, and the lower section 1506 of the trench 1500 is shown at a higher magnification of 200kx. 21A to 21D show that the SiN (B, C) film can exhibit excellent step coverage or conformality. For example, FIGS. 21B-21D illustrate having a thickness of about 23 nm formed on the upper portion 1502 of the trench structure 1500, a thickness of about 23 nm formed on the intermediate portion 1504 of the trench structure 1500, and formation. A SiN (B, C) film having a thickness of about 24 nm on the lower portion 1506 of the trench structure 1500 (eg, about 95% or greater than 95% conformality).

The etching rate of the SiN (B, C) film in a wet etchant (for example, a wet etchant having a ratio of H ₂ O ₂ :HF:H ₂ O of about 5:5:90 by volume) may be about 1.1 nm/min (nm/min) ± about 0.3 nm/min. In certain embodiments, SiN (B, C) film may be immersed in ozone ₍₃ O) prior to exposure to a wet etchant, for example, to increase the etch rate of the film. The etch rate of the SiN (B, C) film immersed in ozone prior to exposure to the wet etchant can have a film etch rate of about 2.2 nm/min ± about 0.5 nm/min. In some embodiments, the etch rate can vary depending on the film composition.

SiN(B,C) films deposited on blanket wafers and analyzed by Rutherford backscatter spectroscopy (RBS) showed just deposition before immersion in a 0.5 wt% HF solution and after immersion for about 2 minutes. The composition of the film is: 20 atom% of bismuth (Si), 35 atom% of nitrogen (N), 20 atom% of boron (B), 18 atom% of carbon (C), and 6 atom% of oxygen (O). 1 atom% chlorine (Cl). The composition of the film after immersing in the HF solution was 19 atom% Si, 30 atom% N, 25 atom% B, 19 atom% C, 7 atom% O, and 1 atom% Cl. RBS analysis showed that the composition of the film may not be significantly affected by the HF immersion process.

Although the present invention has been provided in the context of certain embodiments and examples, those skilled in the art will appreciate that the invention extends to other alternative embodiments and/or uses of the embodiments and Obvious retouching forms and equivalents. In addition, while a number of variations of the embodiments of the invention have been shown and described in detail, other modifications that are within the scope of the invention are readily apparent to those skilled in the art. It is also contemplated that various combinations or sub-combinations may be made in the specific features and aspects of the embodiments, and the various combinations or sub-combinations are still within the scope of the invention. It is to be understood that the various features and aspects of the disclosed embodiments may be combined or substituted with each other to form a variation of the embodiments of the invention. Therefore, it is intended that the scope of the invention should not be limited to the specific embodiments described above.

The headings, if any, provided herein are for convenience only and do not necessarily affect the scope or meaning of the devices and methods disclosed herein.

100‧‧‧Process
102, 104‧‧‧ blocks
200‧‧‧flow chart
202, 204‧‧‧ squares
500‧‧‧ trench structure
502‧‧‧ upper
504‧‧‧middle section
506‧‧‧ lower
700‧‧‧Process Process
702, 704, 706‧‧‧ blocks
800‧‧‧ Process
802‧‧‧ sort
804‧‧‧Process
806, 808, 810, 814, 816‧‧‧ blocks
812‧‧‧Process
1300‧‧‧ trench structure
1302‧‧‧ film
1400‧‧‧ trench structure
1402‧‧‧ upper
1404‧‧‧middle section
Lower part 1406‧‧
1500‧‧‧ trench structure
1502‧‧‧ upper
1504‧‧‧middle section
Lower part of 1506‧‧
A, B, C, D‧‧‧ etching performance curve

The above and other features, aspects, and advantages of the invention are set forth in the description of the embodiments. 1 shows a flow chart of an example of a process for depositing boron and carbon films, in accordance with an embodiment. 2A and 2B show an example of a film stack including boron and a carbon film. 3 shows a flow chart of another example of a process for depositing boron and carbon films, in accordance with an embodiment. 4 is a graph of growth rate of boron and carbon films versus process temperature, in accordance with an embodiment. 5 is a graph showing Fourier transform infrared spectroscopy (FTIR) spectra of boron and carbon films deposited according to one embodiment. 6A to 6D are scanning electron microscope (SEM) images of boron and carbon films deposited on a trench structure having a high aspect ratio. 7 is a graph showing the removal rates of boron and carbon films when boron and carbon films are exposed to a wet etchant, in accordance with certain embodiments. 8 is a graph showing boron and carbon film deposition rates as a function of temperature, in accordance with certain embodiments. 9A is a scanning transmission electron microscope (STEM) image of a cross-sectional view of a boron and carbon film deposited according to an embodiment. Fig. 9B is a table showing the composition of the boron and carbon films shown in Fig. 8A. Figure 10 is a graph showing the borosilicate glass (BSG) film at various depths in the ruthenium layer in embodiments in which boron and carbon films are used as dopant films as described herein. A plot of boron ion concentration by secondary ion mass spectrometry (SIMS) analysis. Figure 11 is a graph showing Fourier Transform Infrared Spectroscopy (FTIR) spectra of aged boron and carbon films exposed to the environment surrounding the clean room. Figure 12 is a table showing optical properties and deposition performance of examples of boron and carbon films according to the examples. Figure 13 shows a flow chart of an example of a process for depositing a tantalum nitride film comprising boron and carbon, in accordance with an embodiment. 14 shows a flow chart of an example of a process for depositing a tantalum nitride film comprising boron and carbon, in accordance with another embodiment. Figure 15A is a graph showing the composition of an example of a tantalum nitride film containing boron and carbon in a deposition process as a function of the percentage of triethylboron (TEB) pulses. Figure 15B is a graph of film growth rate as a function of the percentage of TEB pulses for an example of a tantalum nitride film containing boron and carbon in a deposition process. Figure 16 shows an FTIR spectrum of an example of a tantalum nitride film containing boron and carbon. 17 shows X-ray reflectivity (XRR) data for an example of a tantalum nitride film comprising boron and carbon deposited in accordance with embodiments disclosed herein. Figure 18 is a graph showing the film etch rate as a function of the fraction of TEB pulses for an example of a tantalum nitride film containing boron and carbon in a deposition process. 19A to 19D are SEM images showing the etching performance of an example of a tantalum nitride film containing boron and carbon. 20A to 20D are SEM images showing etching efficiencies of an example of a tantalum nitride film containing boron and a carbon component. 21A to 21D are SEM images showing step coverage of an example of a tantalum nitride film containing boron and a carbon component.

Claims (27)

A method of doping a semiconductor substrate, comprising: depositing boron and a carbon film on the semiconductor substrate in a reaction space by exposing the substrate to a vapor phase boron precursor at a process temperature of 300 ° C to 450 ° C, Wherein the boron precursor comprises boron, carbon and hydrogen; and the boron and carbon film are annealed at a temperature of 800 ° C to 1200 ° C. The method of doping a semiconductor substrate according to claim 1, wherein the vapor phase boron precursor is decomposed on the substrate. The method of doping a semiconductor substrate according to claim 1, wherein the vapor phase boron precursor comprises triethylboron or trimethylboron. The method of doping a semiconductor substrate according to claim 1, wherein the vapor phase boron precursor is supplied to the reaction space together with a carrier gas containing argon. The method of doping a semiconductor substrate according to claim 1, further comprising depositing a ruthenium oxide film on the substrate before depositing the boron and carbon film. The method of doping a semiconductor substrate according to claim 1, wherein the boron and carbon film are directly deposited on the semiconductor substrate. The method of doping a semiconductor substrate according to claim 1, further comprising depositing a boron dopant film on the substrate before depositing the boron and carbon film, wherein the boron dopant film is different from The boron and carbon film, and wherein the boron dopant film and the boron and carbon film are sequentially deposited and between the deposition of the boron and carbon film and the deposition of the boron dopant film The substrate is exposed to ambient air. The method of doping a semiconductor substrate according to claim 1, further comprising maintaining a pressure of 0.5 Torr to 10 Torr in the reaction space during exposure of the substrate to the vapor phase boron precursor. The method of doping a semiconductor substrate according to claim 1, wherein the boron and carbon film have a thickness of at most 5 nm. A method of doping a substrate, comprising: depositing a boron and a carbon film on the substrate in a reaction space by using a chemical vapor deposition process, wherein depositing the boron and carbon film comprises: inerting at a process temperature greater than 300 ° C Exposing the substrate to a vapor phase boron precursor in a gaseous environment; and purging the reaction space after exposing the three-dimensional structure on the substrate to the vapor phase boron precursor; and in a nitrogen atmosphere The boron and carbon films are annealed wherein a cap layer is not formed on the boron and carbon films prior to annealing. The method of doping a semiconductor substrate according to claim 10, wherein the depositing comprises depositing the boron and carbon film on a three-dimensional structure on the substrate. The method of doping a semiconductor substrate according to claim 11, wherein the three-dimensional structure has an aspect ratio greater than 8:1, and wherein the boron and carbon films have a step coverage of greater than 80%. The method of doping a semiconductor substrate according to claim 10, wherein the boron and carbon films have a thickness of up to 5 nm. The method of doping a semiconductor substrate according to claim 10, further comprising depositing a ruthenium oxide film on the substrate before depositing the boron and carbon film. The method of doping a semiconductor substrate according to claim 10, wherein the vapor phase boron precursor is supplied to the reaction space together with a carrier gas containing argon. The method of doping a semiconductor substrate according to claim 10, further comprising performing the annealing at a temperature of 800 ° C to 1200 ° C. A method of depositing a film containing boron and carbon, the film containing boron and carbon deposited on a substrate in a reaction space, and the method of depositing the film containing boron and carbon comprises: a process temperature of 250 ° C to 400 ° C Substituting the substrate with a vapor phase boron precursor to form the boron and carbon containing film on the substrate, wherein the vapor phase boron precursor decomposes on the substrate, and wherein the film has a smaller 30 angstroms in thickness. A method of depositing a film containing boron and carbon as described in claim 17, wherein the boron and carbon containing film has a thickness of less than 15 angstroms. A method of depositing a film containing boron and carbon as described in claim 18, wherein the boron and carbon containing film has a thickness of less than 5 angstroms. A method of depositing a film containing boron and carbon as described in claim 17, wherein the boron and carbon film are substantially resistant to a diluted hydrofluoric acid solution. The method of depositing a film containing boron and carbon as described in claim 17, further comprising: depositing the boron and carbon-containing film in a batch processing reactor. The method for depositing a film containing boron and carbon according to claim 17, further comprising forming yttrium oxide, aluminum nitride, aluminum oxide and nitrogen on the boron and carbon-containing film in the reaction space. At least one of the phlegm. The method for depositing a film containing boron and carbon according to claim 17, further comprising: depositing the boron and carbon on at least one of cerium oxide, aluminum nitride, aluminum oxide and tantalum nitride. Membrane. The method for depositing a film containing boron and carbon according to claim 23, further comprising: forming the yttrium oxide, the aluminum nitride, the aluminum oxide, and the nitriding in the reaction space. At least one of the above. A method of depositing a film containing boron and carbon as described in claim 17, wherein depositing the boron and carbon-containing film comprises a recycling process, wherein the recycling process comprises wherein the substrate and the vapor phase are boron At least two deposition cycles in contact with the precursor. A method of depositing a film comprising boron and carbon as described in claim 25, wherein the recycling process comprises less than 100 of the deposition cycles. A method of depositing a film containing boron and carbon as described in claim 17, wherein the boron-containing and carbon-containing film has a 1-s unevenness of less than 5%.