KR101176668B1 - Low temperature epitaxial growth of silicon-containing films using uv radiation - Google Patents

Abstract

Methods of preparing a cleaning substrate surface for blanket or selective epitaxial deposition of silicon-containing and / or germanium-containing films are provided. Also provided are methods of growing silicon-containing and / or germanium-containing films, both substrate cleaning methods and film growth methods being performed at temperatures of 750 ° C. or lower, typically from about 700 ° C. to about 500 ° C. Cleaning methods and film growth methods include using radiation having a wavelength in the range of about 310 nm to about 120 nm in the processing volume in which the silicon-containing film is grown. The use of such radiation in connection with specific partial pressure ranges for reactive cleaning or film-forming component species enables substrate cleaning and epitaxial growth at lower temperatures than those already known in the art.

Description

LOW TEMPERATURE EPITAXIAL GROWTH OF SILICON-CONTAINING FILMS USING UV RADIATION}

The present invention is directed to an apparatus and method useful for selective and blanket (non-selective) epitaxial growth of silicon-containing films, wherein UV radiation is used to enable epitaxial film growth at temperatures below about 700 ° C. It provides economically adequate film growth rate.

The epitaxial growth of silicon-containing films is becoming increasingly important due to new applications for advanced logic and DRAM devices. In order to ensure that device features are not damaged during manufacture of the device, low temperature processes are a major condition in these applications. Low temperature processes are also important in future industries where feature sizes range from 45 nm to 65 nm, and preventing diffusion of adjacent materials is becoming a decisive factor. Lower process temperatures are required for substrate cleaning both prior to growth of the silicon-containing epitaxial film and during selective or blanket growth of the epitaxial film. Selective growth is such that a silicon-containing film is grown on a substrate surface comprising one or more materials, the silicon-containing film is selectively grown on the surface of the first material of the substrate and minimal growth on the surface of the second material of the substrate. It usually means that this is done or no growth occurs.

Selective and blanket, non-selectively grown silicon-containing epitaxial films and films such as Si, Si _x Ge _1-x , and Si _x Ge _1-x (C) grown at temperatures below about 700 ° C. Modified embodiments of such films are required for many current applications. It may also be desirable to remove the native oxides and hydrocarbons prior to the formation of the epitaxial film achieved at temperatures in the range of about 650 ° C. or less, even if the cleaning time period is short enough. Low temperature processing is also important in providing suitable functional devices, but prevents relaxation of metastable strain layers, prevents or minimizes dopant diffusion, and segregation of dopants or Ge / C in epitaxial film structures. Prevention is also assisted. The suppression of facet formation and short channel effects enabled by low temperature processing (low thermal budget processing) is important for obtaining high performance devices. FIG. 10 is a graph 1000 of conditions required to form an oxide-free silicon surface of the kind required for desirable epitaxial growth of silicon-containing films deposited on the surface (Arrhenius plot, Arrhenius plot). The inverse temperature of the substrate is shown on axis 1002 at ° K ⁻¹ . The corresponding temperature in degrees Celsius is shown on axis 1004 in degrees Celsius. The partial pressure of H ₂ O provided to the process chamber is shown on axis 1006 in Torr. It can be readily seen that raising the substrate temperature above, for example, about 800 ° C. is required to obtain an oxide free silicon surface at 10 ⁻⁶ Torr. Obtaining an oxide-free silicon surface at about 650 ° C. requires a H ₂ O partial pressure of less than 10 ⁻⁸ Torr, which is not practical in terms of equipment cost.

Current techniques for selective and blanket epitaxial growth of doped and undoped Si, SiGe, and SiGe (C) films are typically performed using reduced pressure CVD (called RPCVD or LPCVD). A typical pressure reduction process is a temperature of at least 700 ° C., typically at least 750 ° C., in order to obtain acceptable film growth rates when the precursor compounds for film deposition are SiH ₄ , SiH ₂ Cl ₂ (DCS), Si ₂ H ₆ , GeH ₄ . Is performed in For selective deposition processes, these precursor compounds are combined with additional reagents such as, for example, Cl ₂ , HCl and optionally HBr. Carbon-containing silane precursor compounds such as CH ₃ SiH ₃ may be used as the dopant. Alternatively, inorganic compounds such as, for example, B ₂ H ₆ , AsH ₃ , and PH ₃ may also be used as dopants.

The configuration of blanket Si _x Ge _1-x epi film growth (non-selective growth) from dichlorosilane (DCS) and germane (GeH ₄ ) is shown in FIG. 1. The growth rate of the Si _x Ge _1-x epi film in ohms / min is shown as a function of the deposition temperature and as a function of the ratio of DCS: GeH ₄ in the precursor gas supplied to the deposition process. The configuration relates to the deposition of a film containing from about 20% to about 28% germanium. In order to reduce the variation of the germanium content in the Si _x Ge _1-x epi film deposited at different deposition temperatures, it is necessary to adjust the ratio of Si: Ge ratio in the precursor gas used for the film deposition. 1 is a graph of the kPa / min growth rate of a Si _x Ge _1-x epitaxial film on axis 104 as a function of DCS: GeH ₄ precursor gas flow rate on axis 108 and a temperature of ° C. on axis 102. 100). The data shown in FIG. 1 is generated using a process chamber of the type disclosed herein later, a flow rate for DCS of about 100 sccm, and a flow rate for GeH ₄ that is modified in the form shown. The film forming process shown in FIG. 1 was performed at a process chamber pressure of about 10 Torr. 1 illustrates the problem of reduced Si _x Ge _1-x epi film growth rate at temperatures below about 700 ° C., where the growth rate rapidly decreases from about 400 μs / min at 750 ° C. to about 15 μs / min at 600 ° C. . This sudden decrease in film growth rate at temperatures below about 700 ° C. is due to the fact that film growth is thermally activated and surface reaction is limited.

A similar sharp decrease in film growth rate is found in the selective deposition of silicon-germanium films. The rapid decrease in film growth rate with decreasing temperature may be due to the desorption of SiCl ₂ from the growth film surface, low recombination HCl desorption rate, and the high activation energy required to achieve low surface mobility.

It is generally known in the art that silicon-containing substrates can be cleaned to remove organic materials and native oxides from the substrate surface. In some cases such cleaning includes the use of UV cleaning in a reduced pressure CVD system. This cleaning is performed at a temperature in the range of about 800 ° C. and utilizes irradiation of the substrate by deep UV radiation under hydrogen in a pressure range of 0.002 to 10 Torr. One type of apparatus used to perform the substrate cleaning process is a horizontal cold-wall air-cooled quartz chamber, wherein the backside of the wafer cleaned in the horizontal cold-wall air-cooled quartz chamber is directly heated by an air-cooled tungsten lamp. do. The rise time to 900 ° C. and cooling time to 200 ° C. are typically about 5 seconds and about 20 seconds, respectively. The base pressure of the process chamber is typically in the range of about 2 mTorr. After reaching this pressure, the hydrogen flow is set. Hydrogen flow is generally intended to prevent contamination of the substrate surface during the cleaning process. The cleaning of the sample is performed at 800 ° C., the sample surface is in the hydrogen state, and the sample surface is placed for less than 1 minute for short UV radiation, and the radiation is mostly concentrated at about 253 nm. Subsequently, an epitaxially grown silicon (eg) film is deposited from reactive gases such as HCl and electronic grade SiH ₄ diluted in hydrogen (about 1/1000). Typically the temperature of the substrate during deposition of the epitaxially grown silicon film is at least about 800 ° C. If the processing temperature is above 800 ° C. during film deposition, initial interface defects are generally avoided.

In certain cases, substrate cleaning is performed at higher temperatures at atmospheric pressure. For example, prior to epitaxial silicon film growth, the wafer substrate is raised to a temperature range of 900 ° C. to 1190 ° C., the wafer is treated with a 60 second hydrogen bake, and then to erase the semiconductor oxide from the wafer surface. Etched with HCl doped hydrogen gas for 30 second period. After wafer etching, the chamber was purged with hydrogen, followed by the introduction of HCl gas flow and SiHCl ₃ , followed by sequential epi growth at temperatures ranging from 1,130 ° C. to about 5Φ / min (50,000 μs / min) of silicon film. Growth rates are provided.

Epitaxial growth of silicon has been performed using rapid heat treatment techniques to reduce convective heat losses during film growth. Typically, the reaction gas used for rapid heat treatment includes as a reactive carrier a silicon chloride source (eg, Si _x H _y Cl _z ) mixed with hydrogen. Inert carrier gases such as argon, neon, xenon, or krypton may be added. The process is performed at a silicon substrate temperature of at least 750 ° C. under atmospheric or reduced pressure. When dichlorosilane gas is used as the precursor, it can be said that the gas decomposes when the boundary layer on the substrate surface is heated with SiCl ₂ and H ₂ . SiCl ₂ diffuses to the surface and then reacts with H ₂ to form HCl and silicon. HCl is desorbed through the boundary layer in the chamber in which HCl is carried. Hydrogen carrier gas is added to enhance the deposition rate by providing sufficient hydrogen concentration to provide decomposition of SiCl ₂ into Si and HCl. Pretreatment of silicon substrates typically involves a baking step using 10% hydrogen in argon as the atmospheric environment. The pre-baking temperature is 1050 ° C. for 5 seconds and then 1000 ° C. for 20 seconds. The bake pressure is not specified in the literer. Silicon epi deposition is carried out at 1000 ° C. at a process pressure of 50 Torr and utilizes a reaction mixture of 10% hydrogen and argon / hydrogen gas per volume at 18 slm in dichlorosilane flow at 90 sccm.

Catalyst-assisted growth of monocrystalline silicon layers on silicon substrates during the formation of semiconductor devices has also been disclosed in the art. The single crystal silicon layer is formed on a seeding layer configured with a lattice that matches the single crystal silicon. The seeding layer is formed by CAD (catalyst assisted deposition) during the CVD (chemical vapor deposition) process. Seeding materials such as crystalline sapphire may also be used.

In forming a single crystal silicon layer by CAD using a catalyst, a gas mainly containing silicon hydride is decomposed by contact with a catalyst body heated to 800-2000 ° C., for example, 1600-1800 ° C. It is preferable that a single crystal silicon layer be deposited on the substrate. Silicon hydride refers to a silane such as, for example, monosilane, disilane or trisilane. The catalyst body is at least one material of the form selected from the group consisting of tungsten, thorium oxide, molybdenum, platinum, palladium, silicon, tungsten, including silicon attached metal alumina ceramics. Typically the catalyst material is formed into a coil facing the substrate on the substrate. The catalyst body is a resistance wire that is activated and heated at a temperature below the melting point. Silicon hydride gas introduced, and hydrogen or a doping gas such as B ₂ H ₆ or PH ₃ included as necessary, are introduced to contact the catalyst. By using a catalytic hot filament on the substrate surface and flowing a film-forming precursor gas over the hot filament prior to deposition on the substrate, the substrate on a substrate at a temperature of about 100 ° C.-700 ° C., typically 200 ° C.-600 ° C. It is possible to deposit an epitaxial silicon seed layer. However, contaminants resulting from catalysts, metal contaminants in the membrane are problematic. Without using a catalyst, the silicon film formed over this processing temperature is an amorphous silicon film.

There is a recent description of the deposition of silicon-containing films on mixed substrates using chemical vapor deposition. There is a description of the deposition of Si and SiGe films; However, no data is provided on the exact crystalline composition of the films produced by this method. The process utilizes trisilane (H ₃ SiSiH ₂ SiH ₃ ) to enable deposition of “high quality Si-containing films” on the mixed substrate.

In recent publications, chemical vapor deposition processes at or near the mass transport limits are described using chemical precursors that allow deposition of thin films. The disclosed embodiments relate to the formation of Si-containing and Ge-containing films. Use of higher order precursors, such as trisilane combined with trisilane or digermane, is recommended for replacement of silane precursors, for example.

See also literature that discloses pre-treatment of a silicon substrate surface prior to depositing a silicon epitaxially-grown film on the substrate. In a process referred to as advanced integrated chemical vapor deposition (AICVD) for semiconductor fabrication, the substrate uses hydrogen flowing in the UHV-LPCVD process chamber to remove native oxide from the silicon substrate surface. Prebaked at temperatures ranging from 800 ° C. to 900 ° C. for −30 minutes. Subsequently, medium temperature silicon epitaxial layer growth takes place using a dichlorosilane as the source gas at a thickness in the range of 100 Pa to 300 Pa at a temperature in the range of 600 ° C. to 900 ° C. (usually 700 ° C. to 800 ° C.). Following silicon epi growth, dichlorosilane is replaced with silane gas or other hydrogen-containing gas is supplied to the process chamber and the temperature drops below 400 ° C., the semiconductor substrate surface terminates with hydrogen.

In another method disclosed for removing native oxide layers, hydrogen gas is used as the processing reagent. Laser projection onto the substrate surface is used to enhance the reaction of hydrogen. No specific wavelength for irradiation is mentioned. Clearly, the projected laser provides local heating at the substrate surface.

A review of the background art mentioned above and other techniques known in the semiconductor fabrication arts enables both blanketing and selective deposition of epitaxially grown films containing silicon at temperatures below 750 ° C., preferably below about 700 ° C. There is a continuing need for ways to do this. It may also be carried out at or below the silicon-containing film deposition temperature (in preparation for deposition of the silicon-containing film) so that devices in the substrate on which the film is deposited are not affected by cleaning of the substrate and deposition of the film. A substrate cleaning procedure is required.

The inventors have developed a method of preparing a cleaned and passivated silicon-containing substrate surface for the deposition of epitaxially grown silicon-containing films. The silicon-containing substrate cleaning / passivating method may be used in combination with the method of depositing silicon-containing films, and at least during deposition (and optionally during cleaning and deposition), the substrate surface is exposed to UV radiation. Typically the primary cleaning to remove the bulk of oxygen and organic materials is initially performed using aqueous HF dips (etching) of generally known techniques. This leads to the cleaning / passivation method of the present invention that is used to remove small amounts of residual oxides and to provide the desired surface structure for epitaxial growth of silicon-containing films on the substrate. The cleaning / passivation methods of the present invention are typically performed at temperatures in the range of about 1000 ° C. to about 500 ° C., depending on whether UV radiation is used during the cleaning process. If no UV radiation is used, cleaning and passivation methods are typically performed for as short a time period as possible (typically 2 minutes or less), providing a suitable surface for epitaxial growth. When UV radiation is used and the wavelength of radiation ranges from about 310 nm to 120 nm, preferably from about 180 nm to about 120 nm, radiation is generally applied on the surface of the substrate from a radiation source located adjacent to the substrate surface. The use of UV radiation allows for cleaning and passivation of the substrate surface, which is typically performed at low temperatures ranging from about 700 ° C to about 500 ° C. A hydrogen atmosphere of about 10 Torr or less is typically applied over the substrate surface during cleaning and passivation of the substrate.

Deposition of the silicon-containing film is carried out at temperatures of up to 750 ° C., typically up to 700 ° C., preferably up to about 650 ° C., and typical total pressures in the deposition chamber range from about 1 Torr to about 80 Torr, with UV radiation The wavelength range is about 310 nm to about 120 nm. These allow us to epitaxially grow silicon-epitaxially at lower temperatures with the use of commercially acceptable deposition rates (at least about 60 Hz per minute), temperatures in the range of about 650 ° C., and combinations of specific UV radiation sources and film precursor gases. It can be expected that the containing films can be deposited. Deposition of blanket and selective silicon epi films from precursors comprising structures that may benefit from the use of UV radiation to enhance the growth rate of the film allows for film deposition at lower temperatures. For example, higher order chlorosilanes, bromosilanes, and silanes such as dichlorosilane (DCS) or hexachlorodisilane (HCD) precursors generally provide increased growth rates at lower temperatures. The wavelength of the UV radiation is selected to match the absorption cross section of the particular precursor and to enhance the substrate surface activation, so that the absorption cross section and the substrate surface activation of the precursor are most useful at acceptable processing temperatures. The reactants of germanium-containing precursors with chlorosilanes and silanes can be adjusted to form Si _x Ge _1-x epitaxial films to provide selective deposition on specific substrates as well.

Typically the silicon-containing substrate surface may extend to monocrystalline silicon or silicon-germanium, but to other silicon-containing substrates having the ability to allow epitaxial film growth on the substrate surface.

The cleaning / passivation method and the silicon-containing film growth method do not require the use of a catalyst. Instead, the method is directed to reactive cleaning / passivation and / or film-forming component species to enable epitaxial film growth and substrate cleaning / passivation of the silicon-containing film at temperatures below 750 ° C., typically below 650 ° C. It utilizes the use of UV radiation over a particular wavelength range in combination with a specific partial pressure range for it.

The emission wavelength ranges from about 310 nm to about 120 nm to provide the desired energy to enable reaction at the substrate surface. Wavelengths lower than about 180 nm have been shown to be very effective for the film precursor materials described later herein. Emissions include xenon chloride (λ = 308 nm), krypton fluoride (λ = 248 nm), argon fluoride (λ = 193 nm), xenon (λ = 172 nm), argon (Ar ⁺⁺ ) (λ = 257 nm), and krypton ( excimers of λ = 146 nm); And lamps using xenon (λ = 147 nm), krypton (λ = 117 nm to 124 nm), N ₂ arc (λ = 150 nm) and D ₂ (λ = 121 nm). These are examples of radiation sources and are not considered to be the only radiation sources that can be used. Combinations of UV radiation sources at different wavelengths may also be used.

The inventors found that during selective and blanket deposition of silicon-germanium films, the radiation of these wavelengths decomposes the silicon and germanium hydride and chlorinated silane into excited radicals (not ions) as well as the absorption rate of the precursor material and It has been found that the surface reaction on the substrate is enhanced by increasing the desorption rate of the reaction byproduct. For example, in the selective deposition of a silicon-germanium film, the SiCl ₂ desorption rate (eg), recombinable HCl desorption rate, and surface mobility factors all work to create active points at which species enter.

Since radiation is directed past the layer of constituent gas and reactive species toward the substrate surface by controlling the partial pressure of the constituent gases (which produce wash or film-forming species), more species are formed on the substrate or the substrate The reaction may be induced to react in the vapor state above or to form on the substrate surface or to react on the substrate surface. This allows simultaneous species adsorption and desorption at the substrate surface, allowing optimization of species generation and vapor precursor formation, so that islands of precipitated or agglomerated materials are not formed on the substrate surface. Application of radiation in the wavelength range up to about 170 nm produced high quality epitaxial silicon-containing films at growth rates in the range from about 100 mW / min to 500 mW / min at temperatures ranging from about 500 ° C to about 700 ° C.

The partial pressure of each component gas depends on the task to be achieved and varies for cleaning / passivation and deposition of films of different chemical composition. Detailed data is provided in the Examples section of this specification for various embodiments that are experimentally demonstrated. Those skilled in the art can review the teachings and descriptions herein to provide optimized epitaxially grown silicon-containing films by adjusting the precursor material, partial pressure of component gases, emission wavelengths, and power densities of radiation with minimal experimentation. There will be.

1 shows a graph of the epitaxial growth rate of a silicon / germanium film that does not take advantage of UV radiation during film deposition. The film growth rate is shown in ohms / minute as a function of the rate of flow rate of the precursor material and as a function of degrees Celsius. It is not said that GeH ₄ is the flow rate of a gas that is 1% GeH ₄ in hydrogen, but this is also considered to be true for other embodiments.

2A is a schematic cross-sectional view of a process chamber of the kind that can be used to implement the substrate cleaning method and silicon-containing film deposition method of the present invention.

FIG. 2B is a top schematic of an embodiment illustrating the positioning of a UV radiation source lamp in a process chamber of the type shown in FIG. 2A, in which cooling gases enter into a volume containing UV radiation sources and in FIG. 2A As shown, the exhaust is exhausted to an exhaust device (not shown) in communication with the exhaust device.

2C is a side view of the UV radiation chamber 205 including a processing / reaction volume 218 between the bottom of the quartz UV transmission window 206 and the support pedestal 215 on which the substrate 214 is located. The spacing d between the UV radiation source 208 and the top surface 216 of the substrate 214 is shown.

FIG. 3 shows a graph of the epitaxial growth rate of a blanket deposited silicon-germanium film with and without the advantage of 172 nm emission in a film deposition process chamber for films deposited in the temperature range of 550 ° C. to 750 ° C. FIG. The silane-containing precursor is dichlorosilane, the germanium source is germane, and the 172 nm radiation shows a power density of about 2 mW / cm ² .

FIG. 4 shows a graph of the growth rate of the blanket deposited silicon-germanium film shown in FIG. 3, wherein UV radiation is used as a function of the substrate temperature at which film growth is performed (curve 306).

5 shows a graph of the film growth rate of a selectively deposited silicon-germanium film with and without UV radiation as a function of the flow rate of HCl: GeH ₄ (1% per volume in hydrogen) during the film deposition process. The flow ratio of HCl: DCS + GeH ₄ (1% in hydrogen) is about 0.1 or less, and the deposition becomes a non-selective, blanket Si _x Ge _1-X film growth. The ratio of germanium to silicon in the precursor feed gas is about 1:20, the total precursor gas flow (including hydrogen) ranges from about 15-35 slm, UV radiation is 172 nm wavelength, and power density is about 2 mW / cm ² .

FIG. 6 shows a graph of the percent of germanium in a silicon-germanium film selectively deposited for the data provided in FIG. 5. The percentage of germanium in the Si _x Ge _1-X film represents film growth with and without UV radiation. The germanium percentage of the film is shown as a function of the flow ratio of HCl: GeH ₄ (1% per volume in hydrogen) during the film deposition process. When the flow ratio of HCl: DCS + GeH ₄ (1% in hydrogen) is about 0.1 or less, the deposition becomes a non-selective, blanket Si _x Ge _1-x film growth. The germanium to silicon ratio in the precursor feed gas is about 1:20, the total precursor gas flow (including hydrogen) is about 15-35 slm, UV radiation is 172 nm wavelength, and the power density is about 2 mW / cm ² .

FIG. 7 shows a Si _x Ge _1-x film as a function of flow rate of HCl: GeH ₄ (1% per volume in hydrogen) and as a function of temperature (° C. (650 ° C. and 700 ° C.)) when UV radiation is applied during the film deposition process. A graph of percent change in thickness is shown. When the flow ratio of HCl: DCS + GeH ₄ (1% in hydrogen) is about 0.1 or less, the deposition becomes a non-selective blanket Si _x Ge _1-x film growth. The ratio of germanium to silicon in the precursor feed gas is about 1:20, the total precursor gas (including hydrogen) flow range is about 15-35 slm, UV radiation is 172 nm wavelength, and power density is about 2 mW / cm ² .

FIG. 8 shows a film thickness graph of a blanket deposited silicon-germanium film as a function of applied power in the form of 172 nm radiation, and the effect of the presence of 172 nm radiation is shown for the entire substrate surface in mm from the center of the substrate (wafer). The ratio of Ge: Si in the precursor gas for deposition is about 1:20. UV radiation is at 172 nm wavelength. With reference to FIG. 2A, -150 mm is position A (FIG. 2A), 0 mm is position B, and 150 mm is position C.

9 shows a graph of the percent growth (rate of growth) in the film thickness of a blanket deposited silicon-germanium film as a function of the silicon-containing precursor gas used and a power density of mW / cm ² .

10 shows a graph of the effect of partial pressure of H ₂ O present in a processing chamber at a given temperature depending on the amount of oxide present on the surface of a single crystal silicon substrate. The graph relates to the cleaning of the substrate surface prior to epitaxial growth of the silicon-containing film on top.

As a prelude to the detailed description set forth below, each of the forms "a, an" and "the" used in the description of the invention and the appended claims, unless otherwise indicated in the context, It should be noted that it includes.

The inventors have developed a method of preparing a cleaned and passivated silicon-containing substrate surface for the deposition of epitaxially grown silicon-containing films. The silicon-containing substrate cleaning method may be used in combination with the method of depositing silicon-containing films, and at least during the deposition of the film (and optionally during the period of both cleaning and deposition), the substrate surface is exposed to UV radiation. Typically the cleaning / passivation method of the silicon-containing substrate is performed at a temperature in the range of about 1000 ° C. to about 750 ° C. when no UV radiation is used. In this case, the substrate exposure time is minimized to the extent necessary to allow for the desired epitaxial growth on the substrate surface. When UV radiation is used during the cleaning process, the temperature at which the cleaning and passivation process is performed can be reduced. For example, the processing temperature range may be less than 750 ° C., typically less than 700 ° C. to 500 ° C. Typical overall process pressures in the processing volume surrounding the substrate surface range from about 0.1 Torr to about 80 Torr (typically from about 0.1 Torr to about 30 Torr) of hydrogen. It may also include inert gases present in small amounts.

The general purpose during the cleaning and passivation process is to remove hydrocarbons and oxides from silicon-containing substrates, the presence of which hinders the epitaxial growth of silicon-containing films on the substrate. 10 shows the relationship between the partial pressure of H ₂ O in the processing chamber, the temperature (° K) in the processing chamber, and the presence of oxides on the silicon substrate surface. As shown in FIG. 10, when the temperature is lower than about 750 ° C., partial pressure of H ₂ O in the process chamber in the range of about 10 ⁻⁷ Torr is required to have an oxide-free silicon surface. These pressure conditions lead to fairly expensive device requirements and are difficult to meet.

The inventors have found that by treating a silicon substrate in an atmosphere containing hydrogen in the presence of UV radiation, the temperature in the processing to be performed or the time required for surface cleaning, or a combination of both, can be reduced. Typically, to provide the desired processing window, the total pressure range in the processing chamber is from about 0.1 to about 80 (as mentioned above) during silicon-containing substrate surface cleaning and passivation. The substrate temperature range during processing is from about 550 ° C. to about 750 ° C., typically from about 550 ° C. to about 700 ° C. Typically the power density range of UV radiation is from about 1 mW / cm ² to about 25 mW / cm ² .

When the UV radiation wavelength ranges from about 310 nm to about 170 nm, deposition of the silicon-containing film is carried out at a temperature of 750 ° C. or less, usually 700 ° C. or less, preferably about 650 ° C. or less, and the inventors have a wavelength of less than 170 nm. That is, as development of a UV radiation source providing a wavelength within the range of about 170 nm to about 120 nm is completed, epitaxially while providing a commercially acceptable growth rate at temperatures in the range of about 550 ° C. and possibly lower temperatures. It is expected that a growth film will be deposited. In addition, the use of higher order silane-based precursors that respond appropriately to UV radiation in connection with the easy absorption of reactive species into the substrate surface and the easy desorption of reaction by-products from the substrate surface results in epiemic at lower temperatures. It may also be used to enable tactical film growth. The UV radiation wavelength can be optimally adjusted for a given precursor and substrate activation combination.

Typically the silicon-containing substrate may be monocrystalline silicon or monocrystalline silicon-germanium, but is not limited to these two substrates.

The cleaning / passivation method and the silicon-containing film growth method do not require the use of a catalyst. Instead, the methods can be applied to reactive cleaning / passivation and / or film-forming component species to enable epitaxial film growth and substrate cleaning / passivation of the silicon-containing film at temperatures below 750 ° C., typically below 650 ° C. Use of UV radiation over a particular wavelength range in combination with a specific partial pressure range for the same.

The emission wavelength range that provides the desired energy to enable reaction at the substrate surface is within about 310 nm to about 120 nm, typically within about 180 nm to about 120 nm. The inventors have found that during blanket deposition of silicon-germanium films (and silicon films), the use of UV radiation during film deposition allows for a drop in substrate temperature during deposition of the film at a given deposition rate. The inventors also note that during selective deposition of silicon-germanium films, radiation at these wavelengths not only degrades silicon and germanium hydroxides and chloride silanes into excited radicals (not ions), but also the rate of SiCl ₂ desorption (e.g.) It has been found that by increasing the recombination rate of HCl desorption, and surface mobility, the surface reaction on the substrate can be enhanced to create active sites for the entering species.

By controlling the partial pressure of the constituent gases (which generate clean or film forming species), more species react at the substrate surface and vaporize on the substrate because radiation is directed to the layer of constituent gas and reactive species directed towards the substrate surface. Can be induced to react species. Along with simultaneous species adsorption and desorption at the substrate surface, this allows for optimization of species generation in the gaseous state so that aggregated materials do not form on the substrate surface. High quality epitaxial silicon-containing films were obtained at a growth rate of about 100 kV / min to 500 kV / min in the temperature range of about 600 ° C to about 700 ° C.

Ⅰ. Apparatus for Carrying Out the Invention

Exemplary etching process embodiments disclosed herein are performed in an Epi CENTURA7 integrated processing system available from Applied Materials, Inc. of Santa Clara, California. Features of the device in connection with the present invention are described below; However, other devices known in the industry for epitaxial film growth may be used in carrying out the present invention.

2A is a schematic cross-sectional view of a 200 mm epitaxial deposition chamber 100 used as part of a CENTURA7 integrated processing system. The CENTURA7 integrated processing system is a fully automated semiconductor manufacturing system that uses a modular design that accommodates a single wafer, multi-chamber, 200mm or 300mm wafer. As shown in FIG. 2A, the epi film deposition process chamber includes a 316L stainless steel housing structure 201 that surrounds the various functional members of the process chamber 200. A detailed description of the device can be obtained through the manufacturers, and only the members which are important for understanding the present invention are described herein. The quartz chamber 230 includes an upper chamber 205 that includes a UV radiation source 208 and a lower chamber 224 that includes a processing volume 218. Reactive species are provided to the processing volume 218 and processing byproducts are removed from the processing volume 218. The substrate 214 is located on the silicon-coated graphite pedestal 217, and reactive species are applied to the surface 216 of the substrate 214 along with byproducts that are sequentially removed from the surface 216. The substrate 214 and the processing volume 218 are heated using the infrared lamp 210. Radiation from the infrared lamp 210 travels through the upper quartz window 204 of the quartz upper chamber 205 and the lower quartz portion 203 of the lower quartz chamber 224. Cooling gas for the upper quartz chamber 205 enters through the inlet 211 and exits through the outlet 228 (213). Precursor reactant material and diluent, purge and exhaust gas for the lower quartz chamber 224 enter through the inlet 220 and exhaust 222 through the outlet 238. The outlets 228, 238 are in communication with the same vacuum pump or controlled at the same pressure using separate pumps so that the pressures in the upper quartz chamber 205 and the lower quartz chamber 224 are equalized. In FIG. 2A the UV radiation source 208 is offset from the outlet flange 228 (not shown).

The range of low wavelength radiation used to energize reactive species and to aid in adsorbent adsorption and process by-product desorption from the substrate 214 surface 216 provides for epitaxially grown films of various wavelength combinations. It is typically about 310 nm to about 120 nm, depending on the composition. In the embodiment shown in FIG. 2A, the radiation is provided by an excimer lamp 208 located in the upper quartz chamber 205 and the radiation passes through the UV transmission window 206 to reach the substrate 214. (The UV transmission window may be formed of other UV transmission materials such as, for example, doped synthetic quartz, magnesium fluoride, calcium fluoride, sapphire and lanthanum fluoride.) Excimer lamp 208 in upper quartz chamber 205 The space of) is designed to provide uniform radiation over the surface 216 of the substrate 214. The space “d” between the UV radiation source and the top surface 216 of the substrate 214 can be adjusted to accommodate the requirements for the process parameters required for the particular composition of the film being epitaxially grown. For the embodiments disclosed herein, the space range between the UV source and the substrate 214 top surface 216 is about 5 cm to about 15 cm, typically about 5 cm to about 10 cm. The power density range used is about 1 mW / cm ² to about 25 mW / cm ² , typically about 2 mW / cm ² , to 10 mW / cm ² .

The component gas used to form the substrate surface cleaning / passivation or epitaxially grown silicon-containing film enters the processing volume 218 through the entry port shown at 220 and exits through the port shown at 222. The combination of component gases is typically mixed before entering the processing volume. The total pressure of the processing volume 218 is determined by a valve (not shown) on the outlet port 238 for the flow 222.

The temperature inside the upper quartz chamber 205 and on the UV transmission window 206 enters through the cooling gas (port 211 and enters the port in combination with radiation from the infrared lamp 210 disposed above the upper quartz chamber 204). Flow through 228) within a temperature range of about 300 ° C to about 600 ° C. The temperature of the lower quartz chamber 224 is a blower (not shown) through which the air or other cooling gas is circulated, which enters the port 220 and exhausts to the port 238. And radiation from the infrared lamp 210 under the lower quartz chamber 224 within a temperature range of about 600 ° C to about 300 ° C.

The temperature on the substrate 214 surface 216 may be controlled by setting power to the lower lamp module 210b in the lower quartz chamber 224 or by placing the upper lamp module 210a and the lower quartz chamber on the upper quartz chamber 204. Controlled by setting power to both lower ramp modules 210b in 224.

FIG. 2B shows a schematic top view of one embodiment illustrating the positioning of a UV radiation source lamp in a process chamber of the kind shown in FIG. 2A. Cooling gases enter the lower quartz chamber volume 205 (UV radiation source 208) from the entry port 211 (shown in FIG. 2A). The cooling gases 213 discharged are discharged to the discharge port 228 (shown in FIG. 2A). Discharge port 228 communicates with discharge port 238 from which deposition chamber by-product 222 is discharged, or the pressure at the discharge port is balanced using individual vacuum pumps (not shown) attached to each port. Thus, the pressure of the upper quartz chamber volume 204 becomes uniform with the pressure of the lower chamber volume 224 (shown in FIG. 2A), as previously described. The use of separate pumps to control the gases being exhausted minimizes cross contamination of independent volumes 205 and 204.

2C is a side view of the UV radiation chamber 230 that includes a volume 205 between the UV transmission window 206 and the quartz upper chamber window 204. 2C also shows a process chamber 224 that includes a processing volume 218 present between the UV transmission window 206 and the substrate 214. The distance "d" represents the space between the substrate surface 216 and the UV radiation source. This distance “d” is set to achieve the desired UV radiation density at the surface 216 of the substrate 214.

The process chambers shown in FIGS. 2A-2C can be adapted such that the distribution of infrared heating lamps and excimer lamps associated with the substrate is deformed differently from the illustration. In addition, different process chamber designs may have different requirements. Importantly, the infrared lamp distribution, or other device (s) used to provide heating in the process, provides uniform heating of the substrate and allows precise and accurate control over the substrate temperature. In addition, excimer lamps or other sources of radiation from about 310 nm to about 120 nm should provide uniform radiation of the substrate and be capable of injecting sufficient energy into the gas phase and at the rate of generation of reactive species and commercially viable growth rates at the substrate surface. Corresponding desorption of epitaxial film growth by-products necessary to produce high quality epitaxial growth films should allow adsorption of reactants. As mentioned above, the present data indicate that the power density range at the substrate surface for epitaxial growth of high quality silicon-containing films is 1 mW / cm ² to 25 mW / cm ² . Typical silicon-containing component gases used as a source of epitaxial film growth species include SiH ₂ Cl ₂ , or SiH ₄ , or Si ₂ H ₆ or a combination thereof; A combination of GeH ₄ or Ge ₂ H ₆ is used when a silicon / germanium film is prepared; When selective film deposition is desired, typically HCl or Cl ₂ or HBr or combinations thereof are used as component gas sources of silicon and / or germanium. Typical power densities used for these precursor materials are from about 1 mW / cm ² to about 25 mW / cm ² . Preferably the power density is about 2 mW / cm ² to about 10 mW / cm ² . 2A, the substrate 216 may be rotated relative to the UV radiation source 208 by rotating the shaft 240 such that the pedestal 215 on which the substrate 216 is located rotates. This provides radiation of radial symmetry for the UV radiation source 208. Typically the shaft 240 rotates at a speed ranging from about 12 rpm to about 90 rpm.

To reduce the activation energy of a given thermal process, non-thermal energy may be supplied by ions, electrons or photons (using a wavelength less than about 180 nm when an epitaxially grown silicon-containing film is formed). An important consideration is that for most atoms, ionization occurs for photon energy above about 10 eV. This means that photons with an energy of less than about 10 eV can provide pure quantum effects (excited states of atoms, molecules, and radicals participating in chemical and / or physical processes) so that no adverse effects are found. However, it is considered desirable to use additional energy and a total energy of 10 eV or slightly higher in order to enhance the surface clean / passivation reaction where the native oxide is removed and the dangling bonds are passivated with hydrogen prior to epi growth.

The use of low wavelength photons below 180 nm provides a significant increase in the substrate surface ability to adsorb reactive species while desorbing reaction by-products caused by the formation of silicon-containing epitaxial growth films. The basic principle of operating an excimer lamp capable of forming such low wavelength radiation is Ar ₂ * (λ = 126 nm, 9.84eV), Kr ₂ * (λ = 146 nm, 8.94eV), or Xe ₂ * (λ = 172 nm, Dielectrics such as 7.21 eV) or dielectrics in molecular rare gas halide complexes such as ArF * (λ = 193 nm, 6.42 eV), KrCl * (λ = 222 nm, 5.58 eV), KrF * (λ = 248 nm, 5.01 eV) Radiation decomposition of the excimer (dimer here) state produced by the barrier discharge (silent discharge) is followed. Ar ₂ *, Kr ₂ * and Xe ₂ * excimer lamps provide strong emission at 126 nm, 146 nm, and 172 nm, respectively, and are represented as a potent light source for photon-assisted epitaxially grown silicon-containing film deposition. High energy densities decompose gaseous components into reactive species and enhance surface mobility, while increasing desorption of H ₂ , SiCl ₂ and HCl from the substrate surface.

Higher order silanes and chlorosilanes can be used as the silicon source, including, but not limited to, dichlorosilane, hexachlorodisilane, dibromosilane, and derivatives thereof. GeH ₄ , Ge ₂ H ₆ , GeCl _4, and GeH ₂ Cl ₂ may be used as, for example, germanium sources, without being limited thereto. These precursor sources of silicon and germanium provide acceptable growth rates when the substrate temperature ranges from about 350 ° C. to about 550 ° C., and provides high growth rates when the substrate temperature is about 550 ° C. to about 650 ° C.

By using 172 nm UV radiation to assist the film growth process, a growth rate increase of at least 35% is achieved for the blanket film growth of the 26% Ge-containing SiGe film at a substrate temperature of 550 ° C. This will be explained sequentially with reference to FIG. 4.

Ⅱ. Examples

One Example

Prior to epitaxially growing a silicon-containing film on a substrate, removal of native oxide on the substrate surface affecting the surface lattice structure, termination of dangling bonds with hydrogen, and cleaning for sequential growth of the silicon-containing epi film There is a need to provide a passivated surface. Often, the substrate is a silicon wafer that contains a native oxide on the wafer surface. Natural oxide bulk is removed using a wet chemical process, typically using an aqueous HF dip. Following this natural oxide bulk removal, an in-situ clean / passivation process is performed in the coating deposition chamber to remove residual oxides and hydrocarbons and passivate the substrate surface prior to epitaxial growth of the silicon-containing film. Is used. During the in-situ clean / passivation method, the substrate is exposed to a hydrogen atmosphere in the processing volume simultaneously with the radiation exposure at wavelengths of about 180 nm or less. In the processing apparatus disclosed herein above, the flow rate of hydrogen is 25 slm to 50 slm. The temperature range at the substrate surface is 500 ° C. to 650 ° C. for a time range of about 1 minute to about 5 minutes. The pressure at the processing volume is about 0.1 Torr to about 100 Torr, and typically the pressure range is typically about 5 Torr to about 30 Torr. The power density range is about 2 mW / cm ² to about 25 mW / cm ² , and typically about 2 mW / cm ² to about 10 mW / cm ² . The space ("d") between the substrate surface and the radiation source ranges from about 5 cm to about 20 cm, preferably from about 5 cm to about 10 cm. Typically the treatment time range for the substrate is from about 1 minute to about 5 minutes.

2 Example

3 shows a graph 300 of the epitaxial growth rate of a silicon / germanium film with and without the advantage of 172 nm emission in the film deposition process volume, for films deposited at temperatures in the range of 550 ° C. to 750 ° C. FIG. A substrate temperature of ° C is shown on the scale 302, and a growth rate of kPa / min is shown on the scale 304. Curve 308 represents the film growth rate without taking advantage of the 172 nm emission. Curve 306 represents the film growth rate that takes advantage of the 172 nm emission. When 172 nm radiation is present, the power density at the substrate surface is about 2 mW / cm ² . The silicon-containing component of the deposition process gas is SiH ₂ Cl ₂ , the germanium-containing component is GeH ₄ , and the ratio range of silicon to germanium is about 1:20. The space “d” between the top surface 216 of the substrate 214 and the radiation source 208 (shown in FIG. 2A) is about 5 cm. Process volume 218 is approximately 7500 cc. The total flow rate of process gas into the process volume 218 is about 30 slm. The flow rate of SiH ₂ Cl ₂ is 100 sccm, and the flow rate of 1% GeH ₄ per volume in hydrogen is variable from 300 sccm to 500 sccm (giving 3 sccm to 5 sccm of GeH ₄ ). The pressure in process volume 218 is 10 Torr. The applied power density is 2 mW / cm ² .

3 Example

4 shows a graph 400 of growth rate growth of a silicon-germanium film due to the use of 172 nm radiation in the process volume during film formation. The growth rate is shown as a function of the substrate temperature at which film growth is performed. Process conditions have been described above with reference to FIG. 3. The substrate temperature is plotted on the scale 402 in degrees Celsius, and the increase in growth rate of the silicon / germanium film is plotted on the scale 404, and the curve 406, representing the relationship between them, shows the presence of 172 nm emission in the process volume. It indicates that the advantage has an increasing effect at lower temperatures.

4 Example

FIG. 5 is a graph (500) of the film growth rate of selective silicon-germanium film deposition with and without 172 nm UV radiation in the process volume as a function of the flow ratio of HCl: GeH ₄ (1% per volume in hydrogen). ). When the flow ratio is about 0.1 or less, the deposition becomes a non-selective, blanket Si _x Ge _1-x film growth. The substrate temperature is 650 ° C., the pressure in the process volume is 10 Torr, and the power density is 2 mW / cm ² . The flow rate of SiH ₂ Cl ₂ is 100 sccm, the flow rate of GeH ₄ in hydrogen ranges from about 300 sccm to about 500 sccm, and the volumetric ratio of Si: Ge in the process gas is provided at about 100: 3 to about 100: 5. . The volume flow ratio of HCl: (DCS + GeH ₄ (1% in hydrogen) is shown on scale 502, and the film growth rate of f / min is shown on scale 504. Curve 508 is arbitrary The relationship in the absence of a 172 nm emission input of is shown as a curve 506 shows a relationship where 172 nm radiation is applied at a power density of ² mW / cm ^2. Deposition is more likely with increasing HCl: (DCS + GeH ₄ ) ratio. The volume ratio of HCl or Cl ₂ or HBr to silicon-containing precursor is from about 0.05: 1 to about 50: 1 and at least 0.05: 1.

FIG. 6 is selective formed under the process conditions disclosed with reference to FIG. 5 as a function of the flow ratio of HCl: GeH ₄ (1% per volume in hydrogen) for films formed with and without 172 nm emission in the process volume; A percent graph 600 of germanium in the deposited silicon-germanium films is shown. When the flow ratio is less than about 0.1, the deposition becomes a non-selective blanket Si _x Ge _1-x film growth. The volume flow ratio is shown on scale 602 and the germanium percentage in the silicon / germanium film is shown on scale 604. Curve 608 represents a silicon / germanium film formed without inputting radiation to the process volume. Curve 606 represents the silicon / germanium film formed when 172 nm radiation is provided at a power density of ² mW / cm ² . The germanium content of the films deposited by the process of the invention ranges from about 1% to about 90%, typically from about 5% to about 40%.

5 Example

FIG. 7 shows a graph 700 of film thickness change of a selectively deposited silicon-germanium film as a function of the temperature at which film deposition is performed and the flow ratio of HCl: GeH ₄ (1% per volume in hydrogen). When the flow ratio is less than about 0.1, the deposition becomes a non-selective, blanket Si _x Ge _1-x film growth. The pressure in the process volume is 10 Torr and the power density is 2 mW / cm ² . The flow rate of SiH ₂ Cl ₂ is 100 sccm, the flow rate of 1% GeH ₄ per volume in hydrogen ranges from about 300 sccm to about 500 sccm, and the volumetric ratio of Si: Ge in the process gas is about 100: 3 to about 100: Provided by 5. The volume flow ratio of HCl: (DCS + GeH ₄ (1% in hydrogen) is shown on scale 702, and the film thickness growth increase percentage (indicative of film growth rate) is shown on scale 704. 706 shows the relationship to the substrate temperature of 700 ° C. during film deposition, and curve 710 shows the relationship to the substrate temperature of 650 ° C. during film deposition. It can be seen that it affects the growth rate more.

8 shows a film thickness graph 800 of a blanket deposited silicon-germanium film as a function of the power density of UV radiation applied during film deposition. For example, when UV radiation is applied, it is 172 nm radiation. The effect of providing 172 nm radiation is shown for the entire substrate surface in mm from the center of the substrate (wafer). The spacing from the substrate center in mm is indicated on scale 802, and the silicon / germanium film thickness in ohmsstrong is shown on scale 804. Curve 806 shows the relationship when no 172 nm radiation is provided in the processing volume. Curve 808 shows the relationship when 172 nm emission is provided at a power density of about 1.3 mW / cm ² at the substrate surface. Curve 810 shows the relationship when 172 nm emission is provided at a power density of about ^2.0 mW / cm ² . The other process conditions are essentially the same as those disclosed in connection with FIG. 3, with the substrate temperature at 650 ° C. during film deposition.

The power density can increase substantially above ^2.0 mW / cm ² , and is expected to increase substantially correspondingly with the film growth rate. A suitable upper limit range for applying power density is in the range of about 25 mW / cm ² when the device is a previously disclosed device.

6 Example

9 shows a graph of the percent increase in blanket deposited silicon-germanium film thickness as a function of power applied in 172 nm emission form and as a function of precursor used as a silicon source. The amount of power applied is shown on the scale 902 in mW / cm ² , and the percent film thickness increase is shown on the scale 904. Curve 906 represents the percent increase in film thickness compared to film deposition without increasing UV for SiH ₄ -based processes, and curve 908 shows SiH ₂ Cl when UV radiation is used to increase film growth rate. _The percent increase in film thickness for the _two -based process is shown. It will be appreciated that the film growth rate is faster when the chlorine containing silicon precursor component is used. The substrate temperature is 650 ° C., the pressure in the process volume is 10 Torr, the flow rate of SiH ₂ Cl ₂ is 100 sccm, and the flow rate of GeH ₄ (1% in hydrogen) is 300 sccm. The flow rate of SiH ₄ is 100 sccm, and the flow rate of GeH ₄ (1% in hydrogen) is 300 sccm. These flow rates provide a germanium atom concentration of about 17.5% in the Si: Ge film when the silicon-containing precursor is DCS, and a germanium atom concentration of about 10% when the silicon-containing precursor is SiH ₄ .

The above-described embodiments are not intended to limit the scope of the invention, and those skilled in the art will be able to implement other embodiments corresponding to the scope of the invention claimed below with reference to the above embodiments.

Claims (25)

A method of epitaxially growing a silicon-containing film on a surface capable of epitaxial growth of a silicon-containing film having a desired structure, The method comprises using a lamp-generated radiation having a wavelength in the range of 310 nm to 120 nm transmitted in the processing volume where epitaxial growth of the silicon-containing film is performed, The power density of the radiation is at least 1 mW / cm ² on the surface, and the epitaxial growth of the silicon-containing film is performed at a temperature in the range of 500 ° C. to 700 ° C. and a pressure in the range of 1 Torr to 80 Torr. A method of epitaxially growing a containing film. The method of claim 1, Wherein the method is carried out using radiation having a wavelength range of 180 nm to 120 nm. 3. The method according to claim 1 or 2, Wherein the power density is in the range of 1 mW / cm ² to 25 mW / cm ² . The method of claim 3, wherein And wherein the growth rate of the silicon-containing film is greater than 60 microseconds / minute. 3. The method according to claim 1 or 2, Wherein the silicon-containing film is a silicon-germanium film, wherein the atomic percentage of germanium in the epitaxially grown film is constant within the range of 1% to 90%. 6. The method of claim 5, Wherein the silicon-containing film is a silicon-germanium film, wherein the atomic percentage of germanium in the silicon-germanium film is constant within a range of 5% to 40%. The method of claim 6, Wherein the silicon-germanium film is blanket deposited and the precursor for providing silicon to the silicon-germanium film is selected from the group consisting of silanes, chlorosilanes, and combinations thereof. The method of claim 7, wherein Wherein the precursor is selected from the group consisting of dichlorosilane, dibromosilane, hexachlorodisilane, and combinations thereof. The method of claim 7, wherein And a precursor for providing germanium to the silicon-germanium film is selected from the group consisting of GeH ₄ , Ge ₂ H ₆ , GeCl ₄ , GeH ₂ Cl _2, and combinations thereof. 9. The method of claim 8, And a precursor for providing germanium to the silicon-germanium film is selected from the group consisting of GeH ₄ , Ge ₂ H ₆ , GeCl ₄ , GeH ₂ Cl _2, and combinations thereof. 6. The method of claim 5, The silicon-germanium film is selectively deposited, and the precursor for providing silicon to the selectively deposited silicon-germanium film is silicon selected from the group consisting of silanes, chlorosilanes, bromosilanes, and combinations thereof. -Epitaxially growing the containing film. The method of claim 11, wherein And a precursor for providing silicon to the selectively deposited silicon-germanium film is selected from the group consisting of dichlorosilane, dibromosilane, hexachlorodisilane and derivatives thereof. The method of claim 11, wherein The precursor for providing germanium to the selectively deposited silicon-germanium film is epitaxially grown on a silicon-containing film, selected from the group consisting of GeH ₄ , Ge ₂ H ₆ , GeCl ₄ , GeH ₂ Cl _2, and combinations thereof. How to let. The method of claim 11, wherein During the selective deposition of the silicon-germanium film, HCl or HBr or Cl ₂ , or a combination thereof, is present at a volume ratio of at least 0.05: 1 compared to the precursor, wherein the silicon-containing film is epitaxially grown. 15. The method of claim 14, During the selective deposition of the silicon-germanium film, HCl or HBr or Cl ₂ , or a combination thereof, epitaxially grows the silicon-containing film, which is present in a volume ratio within the range of 0.05: 1 to 50: 1 compared to the precursor. Way. 15. The method of claim 14, And said precursor for providing silicon to said selectively deposited silicon-germanium film is selected from the group consisting of dichlorosilane, hexachlorodisilane and derivatives thereof. 17. The method of claim 16, The precursor for providing germanium to the selectively deposited silicon-germanium film is epitaxially silicon-containing film is selected from the group consisting of GeH ₄ , Ge ₂ H ₆ , GeCl ₄ , GeH ₂ Cl ₂ , and combinations thereof. How to grow. delete delete delete delete delete delete delete delete

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