# Patent

## Title
Methods for depositing an epitaxial silicon germanium layer having a germanium to silicon ratio greater than 1:1 using silylgermane and a diluent

## Abstract

The present application relates to methods for depositing a smooth, germanium rich epitaxial film by introducing silylgermane as a source gas into a reactor at low temperatures. The epitaxial film can be strained and serve as an active layer, or relaxed and serve as a buffer layer. In addition to the silylgermane gas, a diluent is provided to modulate the percentage of germanium in a deposited germanium-containing film by varying the ratio of the silylgermane gas and the diluent. The ratios can be controlled by way of dilution levels in silylgermane storage containers and/or separate flow, and are selected to result in germanium concentration greater than 55 atomic % in deposited epitaxial silicon germanium films. The diluent can include a reducing gas such as hydrogen gas or an inert gas such as nitrogen gas. Reaction chambers are configured to introduce silylgermane and the diluent to deposit the silicon germanium epitaxial films.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
This application relates to methods for depositing heteroepitaxial films in semiconductor manufacturing. More particularly, this application relates to methods for depositing silicon germanium heteroepitaxial films by using silylgermane as a source gas.
2. Description of the Related Art
Silicon germanium (SiGe) films are used in a wide variety of semiconductor applications, including microelectronic devices. One issue that often arises is how to increase the amount of “strain” in an active layer of a device, which leads to increased device performance. A deposited epitaxial layer is said to be “strained” when it is constrained to have a lattice structure in at least two dimensions that is the same as that of the underlying single crystal substrate, but different from its inherent lattice constant. Lattice strain occurs because the atoms in the deposited film depart from the positions that they would normally occupy in the lattice structure of the free-standing, bulk material when the film deposits in such a way that its lattice structure matches that of the underlying single crystal substrate. For example, greater amounts of germanium in an epitaxial layer deposited onto a single crystal silicon substrate or layer generally increase the amount of compressive strain. This strain occurs because germanium in its pure form has a 4% greater lattice constant compared to silicon. Therefore, the higher the germanium content, the greater the lattice mismatch with the underlying silicon.
Strain is in general a desirable attribute for active device layers, since it tends to increase the mobility of electrical carriers and thus increase device speed. In order to produce strained layers on conventional silicon structures, however, it is often helpful to create strain-free, intermediate heteroepitaxial layers for further strained layers that will serve as active layers in semiconductor devices. These intermediate films often comprise a relaxed silicon germanium “buffer” layer over a single crystal semiconductor substrate or wafer surface.
To be an effective buffer layer, the silicon germanium layer should be relaxed. When the thickness of the silicon germanium buffer layer increases above a certain thickness, called the “critical thickness,” the buffer layer begins to relax to its inherent lattice constant, which requires the formation of misfit dislocations at the film/substrate interface. The critical thickness depends on a variety of factors, including growth rate, growth temperature, germanium concentration, and the number of defects within the layer underlying the silicon germanium layer. Once the silicon germanium layer reaches its critical thickness, the layer begins to relax toward its own lattice size and strain is reduced. A silicon germanium layer that has adopted its own natural lattice constant on a nanometer scale through the film may be considered fully relaxed.
Depositing silicon germanium films presents several challenges. Often, it is difficult to achieve a high germanium concentration, whether for maintaining strain or relaxing for use as a buffer, without excessive faults that interfere with electrical operation of the integrated circuit. In addition, it is often difficult to deposit silicon germanium films that are thin and smooth, particularly at low temperatures, to both conserve thermal budget and maintain flatness for integration with subsequent processing. Although numerous source gases are available to create silicon germanium layers, each has its limitations. For example, conventional source gases (e.g. silane) are unable to deposit smooth homogeneous films of low thickness at low temperatures. These source gases often result in films with high surface roughness due to nucleation islands.
More exotic source gases, such as SiH3GeH3, (H3Ge)2SiH2, (H3Ge)3SiH and (H3Ge)4Si have been used to deposit silicon germanium layers. One of the perceived advantages for such gases, containing both germanium and silicon, is that the intrinsic ratio of Si:Ge within the compound is thought to strongly influence the ratio of Si:Ge in the deposited film, permitting wider process windows for a given desired ratio. However, these source gases are costly, lack the flexibility of conventional precursors, and often entail significant hardware adjustments and tuning that have not generally been found worthwhile compared to the perceived benefits of these precursors.
SUMMARY OF THE INVENTION
Briefly stated, the embodiments described herein provide methods and apparatuses for depositing a smooth, germanium-rich epitaxial film by introducing silylgermane as a source gas into a reactor at relatively low temperatures. Amounts of a diluent can be varied to modulate levels of germanium incorporation into the epitaxial silicon germanium film. Examples of diluents include reducing agents, such as hydrogen gas. In some embodiments, one or more inert gases such as nitrogen gas, can be used as a diluent to control silylgermane partial pressures, thereby modulating ratios of Ge: Si in the resultant film to be above 1:1.
Methods of film deposition are described and comprise providing a semiconductor substrate into a reaction chamber. The substrate is placed on a susceptor in the reaction chamber. A precursor comprising silylgermane (SiGeH6) is introduced to the reaction chamber to deposit an epitaxial silicon germanium layer on the substrate comprising greater than 55 atomic % germanium by volume.
Additional methods of film deposition are provided comprising providing a substrate into a reaction chamber and placing the substrate on a susceptor in the reaction chamber. Silylgermane gas is introduced into the reaction chamber to deposit an epitaxial silicon germanium layer on the substrate. In addition to the silylgermane gas, a diluent is introduced into the reaction chamber to modulate the level of germanium incorporation in the deposited epitaxial silicon germanium layer to be greater than 55 atomic % germanium.
Reaction chambers for depositing silicon germanium films are also provided. In some embodiments, a reaction chamber includes a reaction gas inlet and a reaction gas outlet defining a gas flow path therebetween. The reaction chamber includes a support for supporting a substrate within the gas flow path in the reaction chamber. The reaction chamber further includes a gas line communicating silylgermane gas between a container storing silylgermane and the reaction chamber and a gas line communicating H2 gas between a container storing H2 gas and the reaction chamber. The reaction chamber includes a control system programmed to supply the silylgermane gas and H2 gas into the reaction chamber.
In one embodiment, H2 is stored in the same container as silylgermane. In one embodiment, H2 is supplied from a separate container and controls are provided for modulating the ratio of silylgermane to hydrogen.



BRIEF DESCRIPTION OF THE DRAWINGS
These and other features, aspects and advantages of the various devices, systems and methods presented herein are described with reference to drawings of certain embodiments, which are intended to illustrate, but not to limit, such devices, systems, and methods. The drawings include nine figures. It is to be understood that the attached drawings are for the purpose of illustrating concepts of the embodiments discussed herein and may not be to scale.
FIG. 1A illustrates a schematic view of a reaction chamber according to embodiments of the present application.
FIG. 1B illustrates a schematic view of another reaction chamber according to embodiments of the present application.
FIG. 2 illustrates a cross-sectional view of a substrate and a germanium-containing epitaxial layer deposited thereover according to embodiments of the present application.
FIGS. 3A-3D illustrate cross-sectional views of a substrate at various stages of a deposition process with corresponding flow chart according to embodiments of the present application.
FIG. 4 is an x-ray reflectance graph characterizing a layer deposited under certain processing conditions according to one embodiment of the present application.
FIG. 5 illustrates micrographs of a silicon germanium surface area formed under certain processing conditions according to one embodiment of the present application.



DETAILED DESCRIPTION OF EMBODIMENTS
Methods and apparatuses are provided for depositing a smooth silicon germanium (SiGe) epitaxial layer having controllable germanium content over a substrate in a reaction chamber. In some embodiments, a source gas comprising silylgermane (SiGeH6) is introduced into a reaction chamber to deposit a silicon germanium layer having a high percentage of germanium. The term “substrate,” as used herein, can refer to a bare wafer or to a workpiece with existing layers.
According to methods described herein, a silicon germanium layer having a high percentage of germanium (e.g., greater than 55 atomic %) can be deposited. In some embodiments, the deposited silicon germanium layer can serve as a strained layer that produces a compressive lattice strain on an underlying layer. This lattice strain results due to the natural lattice constant of the silicon germanium layer being higher than the natural lattice constant of the underlying substrate. In other embodiments, rather than serving as a strained layer, the deposited silicon germanium layer serves as a relaxed buffer layer for subsequently deposited, overlying strained layers. As a buffer layer, the silicon germanium layer serves as a template for overlying strained layers that help to increase the carrier mobility in the underlying substrate. In some embodiments, an overlying strained layer above the deposited silicon germanium layer comprises a strained silicon or strained germanium layer, which is forced to align with the lattice constant of the relaxed silicon germanium buffer layer.
Various source gases and liquids can be used to deposit a silicon germanium layer having a high germanium concentration. In some embodiments, silylgermane is the source gas. While silylgermane gas is rarely used in conventional deposition processes due to the difficulty in manufacturing the gas and its relatively limited shelf-life, it has been found that using silylgermane provides a number of particular advantages. One advantage of using silylgermane is cost savings, as it is cheaper to produce than many other complex source gases. A second advantage of using silylgermane is the ability to deposit smooth, high-quality silicon germanium films at very low temperatures. This is particularly advantageous for achieving higher strain on a reduced thermal budget. Moreover, such smooth, low temperature film depositions can produce greater than 50% germanium epitaxial. Surprisingly, it has been found that the germanium context can be modulated above the 1:1 ratio of Ge:Si in the precursor, particularly by controlling partial pressures and/or reduction by introducing a diluent with the silylgermane gas. The term “diluent,” as used herein, can refer to an inert gas, such as nitrogen or argon gas, or to a reducing gas, such as hydrogen gas. In some embodiments, the silylgermane is stored with the diluent; in other embodiments, the diluent is separately supplied.
Process Reactor
FIGS. 1A and 1B schematically illustrate chemical reactors 200 including a reaction chamber 205 and one or more containers for source gases, for which the methods disclosed herein have particular utility. FIG. 1A illustrates one embodiment of a CVD reaction chamber 205 having quartz process walls 208. The reaction chamber 205 includes a plurality of radiant heat sources 215 supported outside the chamber to provide heat energy to the chamber 205 without appreciable absorption by the quartz chamber walls 208. These heat sources can include an assembly of elongated tube-type radiant heat elements, each of which may be a high intensity tungsten filament lamp having a transparent quartz envelope containing a halogen gas, such as iodine. While the preferred embodiments are described in the context of a “cold wall” CVD reactor for processing semiconductor wafers, it will be understood that the processing methods described herein will have utility in conjunction with other heating systems, such as those employing inductive or resistive heating.
A substrate 202, preferably comprising a silicon wafer, is shown supported within the reaction chamber 205 upon a susceptor or wafer support structure 220. In some embodiments, by using the heat sources 215, the substrate 202 can be quickly heated in a hydrogen bake or similar oxide reduction step to rid the substrates of contaminants. The heat sources 215 can also be used to control the substrate 202 to the desired deposition temperature at which a silicon germanium layer can be deposited thereover. In some embodiments, the heat sources 215 are used to first heat the substrate to a temperature of above 600° C. or above 700° C. in a bake step to rid the substrate of contaminants, such as carbon and native oxide. The substrate can be subsequently cooled to a reduced temperature (e.g., between 300° C. and 475° C.) suitable for depositing a silicon germanium film. In other arrangements, chemical etchants can replace or augment the high temperature bake step.
The illustrated reaction chamber 205 includes an inlet port 230 which can include gas injectors for the injection and distribution of source gases and/or carrier gases. The inlet port 230 leads to a gas line 235. In addition to the inlet port, an outlet port 250 can be found on the opposite side of the chamber 205, forming a gas flow path therebetween. While not shown, a vacuum pump is preferably connected to the outlet 250. In some embodiments, the wafer support structure 220 is positioned between the inlet 230 and outlet 250 and in the gas flow path, as in the illustrated laminar, horizontal flow arrangement. In other arrangements, precursors can be provided with radial symmetry over the wafer (e.g., by a showerhead) and/or by backfill and soak. In some embodiments, the reaction chamber 205 can also be connected to a liquid bubbler (not shown) so that liquid sources can also be used to deposit films in the chamber 205.
The gas line 235 is connected to a container 262, which is used to house a source gas or liquid. As shown in FIG. 1A, the source gas comprises silylgermane, which is packed under pressure with hydrogen gas (H2). In other embodiments, the silylgermane gas is stored with a selected mixture of inert gas (e.g., N2, Ar, Kr, Ne, He) and hydrogen. In still other embodiments, the silylgermane is stored with an inert gas, and hydrogen is provided separately during operation.
Without being limited by theory, it is believed that the addition of at least some diluent (e.g., inert gas or reducing gas) mixed with the silylgermane helps to deposit a silicon germanium film with high germanium content, particularly higher than 50 atomic % Ge. For embodiments in which silylgermane is stored with hydrogen as a reducing gas, or at least part of the reducing gas in the container, some amount of precursor decomposition within the container 262 can aid in increasing germanium content in deposited epitaxial films above the 1:1 ratio intrinsic in the precursor. In particular, germanium concentration in epitaxial silicon germanium films was found to be higher than 55 atomic % when silylgermane was stored with hydrogen. The container 262 had silylgermane diluted to 0.5% in hydrogen, a container volume 16 L, and was provided with an initial pressure of about 1600 psi. For embodiments in which silylgermane is stored with hydrogen (with or without additional inert gas diluent), the volume ratio of silylgermane in the container 262 to hydrogen in the container is typically within the range of 1:1000 to 1:20, more particularly of about 1:250 to 1:100.
In other embodiments, the silylgermane can be stored with an inert or hydrogen gas as the diluent. In some embodiments in which silylgermane is stored with nitrogen (with or without additional inert gas diluent), the volume ratio of silylgermane in the container 262 to nitrogen in the container can be within the same range as that of silylgermane to hydrogen discussed above. The germanium content can be modulated by controlling the partial pressure of silylgermane during deposition, which can be influenced by the diluent as stored and any separately supplied diluent or carrier gas.
As shown in FIGS. 1A and 1B, the reactor 260 includes a control system 292 programmed to supply silylgermane gas and H2 gas into the reaction chamber 205. In some embodiments, the control system 292 is connected by electrical lines to the heat sources 215 and to control devices (e.g., valves, mass flow controllers, etc.) along the pipes (e.g., 235, 255 and 266) that are used to deliver source gases into the reaction chamber 205. The control system 292 provides various memory, programming and processing functions. In some embodiments, these functions assist in modulating the amount of silylgermane gas relative to the amount of H2 gas provided into the chamber 205.
FIG. 1B illustrates another embodiment of a reactor 200. The reaction chamber 205 includes an inlet 230 and outlet 250. The inlet 230 is connected via a gas line 270 to an inlet manifold 240. The inlet manifold 240 is connected via a gas line 245 to a mass flow controller (MFC) 265, which is connected by another gas line 266 to the first container 262. The inlet manifold 240 is also connected via a gas line 255 to a second container 258. While illustrated in parallel, the second container 258 can alternatively be connected in series upstream of the first container 262 and serve as a carrier gas drawing and entraining precursor from the first container 262.
As shown in FIG. 1B, the first container 262 houses silylgermane gas and an inert gas. In the illustrated embodiment, hydrogen gas is stored separately from the silylgermane gas in a second container 258. The second container 258 is connected via the gas line 255 to a second mass flow controller 275, which is connected via a gas line 278 to inlet manifold 240. The hydrogen gas serves as a carrier or diluent gas, and is supplied into inlet manifold 240 and ultimately into the reaction chamber 205. Hydrogen also serves as a reducing gas to aid decomposition of the silylgermane during deposition. The parallel lines with separate mass flow controllers 265, 275 allow the volume ratio of silylgermane to hydrogen supplied to the reaction chamber 205 to be modulated, such that the ratio is typically within the range of 1:1000 to 1:20, more particularly between 1:250 and 1:100. The skilled artisan will appreciate that the ratio of silylgermane to hydrogen can alternatively be controlled by other metering devices. In some embodiments, the hydrogen gas can also react with other gases (e.g., chlorine-based gases) to activate etching reactions in selective deposition. The reactor in FIG. 1B provides the hydrogen gas in a separate container from the silylgermane gas and allows for wafer-to-wafer control over the film composition. Instead of or in addition to any hydrogen within the precursor source container 262, a separate supply of hydrogen gas from its own source makes it easier to control the ratio of silylgermane relative to hydrogen, and therefore, allows for greater control over the film deposition process and a greater range of germanium percentages in silicon germanium films. While second container 258 illustrates hydrogen as a supplemental inert gas, other gases can also be provided instead of or in addition to hydrogen, including triethyl boron (TEB), alcohols, carboxylic acids and aldehydes.
In the embodiment shown in FIG. 1B, the first container 262 contains silylgermane gas and a non-reactive, inert gas. The inert gas can include argon (Ar), helium (He), neon (Ne), nitrogen (N2), or other suitable gases. In some embodiments, the percentage of the silylgermane gas in the first container 262 is between about 0.1% and 10%.
As shown in FIG. 1B, the first container 262 is connected via the gas line 266 to the first mass flow controller (MFC) 265, which is coordinated at a gas panel. Process gases are communicated to the inlet 230 in accordance with directions programmed into the control system 292 for the first and second mass flow controllers 265, 275 or other metering device(s) before being distributed into the reaction chamber 205. The metering device can help control the film deposition rate by controlling the introduction of silylgermane and other source gases into the chamber. For example, in some embodiments, the first mass flow controller 265 can control the flow rate of silylgermane into the chamber, such that it flows between a certain flow rate (e.g., between approximately 70 sccm and 175 sccm). Associated with the flow rate is the deposition rate of silicon germanium, which in some embodiments, is between approximately 8 and 12 nm/hour.
A separate carrier gas (not shown) can also be provided to deliver the silylgermane from the first container 262 to the reaction chamber 205. In some embodiments, the carrier gas comprises hydrogen and serves as the reducing agent and can be made highly pure, due to its low boiling point, and is compatible with the deposition of silicon germanium. In this case, the second container 258 supplying hydrogen can be positioned upstream of the first container 262, as mentioned above. Other suitable carrier gases can include inert gases such as argon (Ar), helium (He), neon (Ne), and nitrogen (N2).
In some embodiments, supplemental reactant sources can be supplied, via gas lines, into the reaction chamber 205 to further aid in modulating silicon or germanium concentration in the SiGe layer, electrically doping or attaining selectivity. Such supplemental sources can include etchants (e.g., HCl, Cl2), dopant sources (e.g., arsine, phosphine, borane), and silicon or germanium sources that will decompose at the substrate temperature of operation (e.g., germane, trisilane). One skilled in the art will appreciate that the addition of supplemental sources besides silylgermane gas is optional, and that using silylgermane gas without such supplemental sources allows for a film having a high germanium content. Moreover, while supplemental silicon and germanium sources may aid modulation of germanium content for the embodiment of FIG. 1A, they are unnecessary for FIG. 1B, which can modulate germanium content without supplemental silicon or germanium sources.
The reaction chamber 205 can also communicate with containers for etchants that can be used to clean unwanted film deposits on reactor walls, such as fluorine-based etchants, and optional plasma sources for more effective cleaning at low temperatures.
Processes
Methods for depositing silicon germanium films having high germanium concentration are described below. FIG. 2 illustrates a strained silicon germanium layer 110 deposited over a silicon substrate 100. In contrast, FIGS. 3A-3D and the accompanying flow chart therein illustrate a silicon germanium layer 310 deposited over a substrate 300 that serves as an intermediate buffer layer for an overlying strained or relaxed layer 320.
In accordance with FIG. 2, the substrate 100 is first provided into a reaction chamber. The substrate 100 can include a silicon wafer, a silicon-on-insulator wafer, or a substrate with an existing layer deposited thereover.
In some embodiments, before depositing an epitaxial layer over the substrate, the surface of the substrate is cleaned to remove contaminants. The substrate can be cleaned by heating the substrate 100 in a bake step to a temperature greater than about 600° C. or greater than about 700° C. and/or use etchants in situ or ex situ. Following the cleaning of the substrate 100, the substrate 100 can be brought to an appropriate deposition temperature between about 250° C. and 525° C., and preferably between about 300° C. and 475° C., in preparation for a chemical vapor deposition process. This low deposition temperature range of between about 300° C. and 475° C. is ideal for silylgermane gas, but is generally too low for standard source gases such as silane and disilane to operate due to their greater thermal stability. In some embodiments, the temperature of the substrate is maintained above 350° C. during the entire deposition process. The pressure in the reaction chamber is preferably also controlled. In some embodiments, the pressure is kept at about atmospheric pressure, while in some embodiments, the pressure is kept between about 50 Torr and 100 Ton in the reaction chamber during deposition.
Once the substrate is at a temperature between about 300° C. and 475° C., a source gas comprising silylgermane can be introduced into the chamber to deposit a germanium-containing film (e.g., a germanium film or a silicon-germanium film) on the substrate. In addition to the silylgermane source gas, a diluent to aid decomposition of silylgermane at the deposition temperature can be introduced into the chamber. In the illustrated embodiments, the diluent comprises a reducing gas such as hydrogen gas. The silylgermane source gas and the hydrogen gas can be stored together in the same bottle (as in FIG. 1A), while in other embodiments, the silylgermane source gas can be stored separately from the hydrogen gas (as in FIG. 1B). In some embodiments, silylgermane source gas can be stored with hydrogen gas as a diluent in a first bottle, with or without additional inert diluent, while a separate source of hydrogen gas is stored in a second bottle for modulating the ratio of silylgermane to hydrogen in operation. It has been found that by introducing silylgermane with an amount of hydrogen, it is possible to modulate the percentage of germanium in a deposited germanium-containing film by introducing hydrogen gas (as stored with the silylgermane gas, from a separate container, or both) and controlling the ratio of silylgermane to hydrogen. By introducing hydrogen gas in addition to the silylgermane gas, it has been found that germanium-containing films can be deposited having a germanium percentage as high as 90%. In some embodiments, the silylgermane diluted to 0.5 vol. % can be introduced at a flow rate between about 70 sccm and 175 sccm. In some embodiments, the flow of the silylgermane remains relatively constant, while in other embodiments, the flow of the silylgermane can vary during the deposition process. In some embodiments, in addition to the silylgermane source gas, a hydrogen gas flow can also be provided at a flow rate between about 10 sccm and 5 slm.
By using silylgermane and a reducing gas, a smooth silicon germanium film 110 having a high germanium percentage can be deposited on the silicon substrate 100. In some embodiments, the silicon germanium film will have a surface roughness of 5 nm rms, more preferably of 3 nm rms or less. In some embodiments, the surface roughness is between 1 and 3 nm rms. A silicon germanium film can be deposited having a high germanium percentage between about 55% and 90%, more preferably between 65% and 85%, thereby resulting in a high-degree of strain. In some embodiments, when the silylgermane source gas and hydrogen gas are stored in the same bottle and flowed together into the reaction chamber, a germanium-containing film can be deposited having a germanium content between about 60% and 85%. In some embodiments, when the silylgermane source gas and hydrogen gas are stored in separate containers and flown separately into the reaction chamber, a germanium-containing film can be deposited having a germanium percentage between about 55% and 90%. As pure germanium has a lattice constant that is about 4% greater than that of pure silicon, the epitaxial layer 310 will at least initially be in compressive strain with respect to the underlying silicon layer 300 unless deposited to greater than the critical thickness.
At the temperature ranges described above (e.g., between about 300° C. and 475° C.), the rate of deposition of the silicon germanium film 110 can be high. In some embodiments, the rate of deposition is about 10 nm/hr. This rate can be controlled by controlling the flow rate of the silylgermane source gas (e.g., by using the mass flow controller), as well as by controlling other parameters, such as the temperature of the wafer. In some embodiments, the deposited silicon germanium film 110 is a thin film that is less than 10 nm in thickness such that it generally remains strained at the preferred deposition temperatures. In other embodiments, the deposited silicon germanium film 110 is a thicker film that is 10 nm or greater. While thinner films are generally strained and thicker films generally more relaxed, the amount of strain in the film will depend on a number of factors, including the crystal structure of the starting substrate and deposition temperature. In addition, the critical thickness of a film can also vary based on underlying substrate quality, germanium content and chamber conditions. In some embodiments, the silicon germanium film 110 will have a critical thickness at the deposition conditions of approximately 10 nm, such that the film 110 is strained at a thickness beneath about 10 nm, while it is partially or fully relaxed at thicknesses greater than or equal to about 10 nm. As noted above, the critical thickness of the film will be dependent on temperature, such that at temperatures of approximately 300° C., a film of about 10 nm and a particular concentration of Ge will be strained, while at temperatures of approximately 450° C., a film of the same thickness and germanium concentration will be relaxed. One skilled in the art will appreciate that relaxation of a strained layer does not occur automatically, but rather on a continuum, based on a number of factors, including film thickness composition and temperature.
In contrast to the strained silicon germanium layer 110 found in FIG. 2, FIGS. 3A-3D (with accompanying flow chart) illustrate a silicon germanium layer 310 that serves as an intermediate buffer layer for a subsequently formed overlying layer 320. The process illustrated includes providing a semiconductor substrate 300 into a reaction chamber, heating the substrate 300 to a temperature between about 350° C. and 475° C., depositing a silicon germanium epitaxial layer 310 over the substrate by introducing a silylgermane source gas along with stored or co-flowed reducing gas, allowing the silicon germanium epitaxial layer 310 to relax, and depositing a second epitaxial layer 320 over the relaxed silicon germanium epitaxial layer 310.
As shown in FIG. 3A, a semiconductor substrate 300 is provided into the reaction chamber. After providing the substrate 300 to the chamber, the substrate 300 is heated to between about 350° C. and 475° C. The substrate 300 can be maintained at a constant temperature between about 350° C. and 475° C. during the entire deposition process.
As shown in FIG. 3C, once the substrate 300 is heated to between about 350° C. and 475° C., a silicon germanium epitaxial layer 310 can be deposited over the substrate 300 by introducing a silylgermane source gas. Once the silicon germanium epitaxial layer 310 reaches a certain thickness above the critical thickness for the conditions and [Ge], the flow of the silylgermane source gas is stopped. Preferably, the silicon germanium epitaxial layer 310 is allowed to fully relax before serving as an effective intermediate buffer layer. For example, for some particular concentration of Ge in the film, a 10 nm silicon germanium film can be fully strained at 300° C., partially relaxed at 450° C., and fully relaxed at 500° C.
As shown in FIG. 3D, after the silicon germanium epitaxial layer 310 has been allowed to relax, a second heteroepitaxial layer 320 can be deposited thereover. Once the silicon germanium layer is in its relaxed state, it can serve as a buffer layer for upper strained layers, such as strained III-V material layers, or tensile strained silicon or compressively stressed pure germanium. In some embodiments, the silicon germanium layer can serve as a buffer layer for overlying relaxed layer(s). In one embodiment, a silicon germanium buffer layer is deposited that has a high germanium composition (e.g., 80 atomic % germanium), while a second epitaxial layer is deposited thereover that is of even higher germanium composition (e.g., 100 atomic % germanium).
By using the deposition methods described above, a germanium-containing film can be deposited with minimal coating of reactor surfaces. Conventional deposition processes often require frequent cleaning of the reaction chamber. By using silylgermane as a source gas, ratios of deposition on chamber walls vs. deposition on substrates are reduced, thus requiring reduced frequency and/or duration of cleaning. For example, in one embodiment in which silylgermane gas is used as a source gas at a temperature of 500° C. for 60 minutes, there is very minimal deposition on surfaces of the reaction chamber.
EXAMPLES
Using the methods described herein under various process parameters, it is possible to deposit a high quality silicon germanium layer having high germanium concentration that serves as an active layer or an intermediate buffer layer by using silylgermane source gas in combination with hydrogen or other reducing gas.
Example 1
In one embodiment, a substrate was provided in a reaction chamber. The substrate was heated to a temperature of about 450° C., while the pressure in the reaction chamber was kept at about 100 Torr. Silylgermane gas, stored with hydrogen gas as a diluent, was flowed into the reaction chamber along with 20 L of hydrogen carrier gas. The silylgemermane was introduced into the reaction chamber at three different flow rates: 100 sccm, 150 sccm and 180 sccm, resulting in the deposition of silicon germanium layers having 64 atomic %, 67 atomic % and 70 atomic % germanium percentage, respectively.
Example 2
FIG. 4 is an x-ray reflectance graph showing the results of a deposition under processing conditions according to one embodiment of the present application. In a reaction chamber, a substrate was provided. The substrate was heated to a temperature of about 300° C., while the pressure in the reaction chamber was maintained at approximately 100 Torr. A source gas comprising 0.5% silylgermane in H2 was introduced at a constant flow rate of approximately 175 sccm for 60 minutes to deposit a silicon germanium layer.
To determine the percentage of germanium in the deposited silicon germanium layer, an x-ray reflectance (XRR) test was performed. XRR allows the density of the SiGe film to be determined, which can then be used to determine approximate germanium percentage in a deposited film. Using XRR, it was determined that the deposited silicon germanium layer has a density of 4.4 g/cm3. Once the density is determined, the density table (shown below as Table A) can be used to determine the corresponding germanium percentage in the deposited layer. The deposited silicon germanium layer, having a density of 4.4 g/cc, was therefore found to have a corresponding germanium percentage of about 70 atomic %. Thus, the deposited silicon germanium layer had a high germanium percentage and exhibited increased strain over conventionally deposited silicon germanium layers.










TABLE A







Approx.[Ge]
SiGe Density



(%)
(g/cm3)



















0
2.328



10
2.6302



20
2.9324



30
3.2346



40
3.5368



50
3.839



60
4.1412



70
4.4434



80
4.7456



90
5.0478



100
5.35










Example 3
A chemical vapor deposition took place in a reaction chamber at a temperature of about 450° C. and a pressure of 100 Torr. Silylgermane was introduced at 100 sccm for approximately 30 minutes, resulting in the deposition of a silicon germanium layer. Micrographs were taken of the surface of the silicon germanium layer at 5× and 100× magnification and are shown in FIG. 5. As shown in FIG. 5, even at 100× magnification, the surface of the silicon germanium layer was nearly featureless, which supports that the use of silylgermane as a source gas resulted in the deposition of a smooth epitaxial layer of high quality.
Besides experiments performed at the reaction pressure of 100 Torr, other experiments were also performed at atmospheric pressure. While the experiments at atmospheric pressure resulted in a faster deposition rate of a germanium-containing film, the resulting films (all of which had greater than 50 atomic % germanium) had greater texture (roughness) than those silicon-germanium films deposited at 100 Torr.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For example, while FIG. 1B illustrates silylgermane stored with inert gas and a separate reducing gas source, the skilled artisan will appreciate that a separate inert gas can instead be used in container 258; container 262 can include reducing gas in place of or in addition to inert gas; and various other combinations will be appreciated in view of the teachings herein. Thus, it is intended that the present invention cover the modifications and variations of this invention provided that they come within the scope of the appended claims or their equivalents.

## Claims

1. A method for depositing an epitaxial layer comprising:
providing a semiconductor substrate into a reaction chamber;
placing the substrate on a susceptor in the reaction chamber;
introducing silylgermane (SiGeH6) gas to deposit an epitaxial silicon germanium layer in the absence of germanium sources other than silylgermane; and
introducing a diluent to the reaction chamber to modulate the level of germanium incorporation in the deposited epitaxial silicon germanium layer to have between 60 atomic % and 85 atomic % germanium.

2. The method of claim 1, wherein introducing comprises maintaining the substrate at a temperature between 350° C. and 475° C.

3. The method of claim 1, wherein introducing comprises forming the silicon germanium layer to a thickness less than 10 nm.

4. The method of claim 1, wherein introducing comprises forming the silicon germanium layer as a strained layer.

5. The method of claim 1, wherein introducing comprises forming the silicon germanium layer to have a film surface roughness of 5 nm rms or less.

6. The method of claim 1, wherein introducing comprises forming the silicon germanium layer as a relaxed buffer layer, further comprising depositing a strained heteroepitaxial active layer over the silicon germanium layer.

7. The method of claim 1, wherein introducing comprises forming the silicon germanium layer to have a thickness greater than its critical thickness.

8. The method of claim 1, wherein introducing comprises maintaining the reaction chamber at a pressure between 50-100 Torr.

9. The method of claim 1, wherein introducing comprises flowing hydrogen gas as the diluent.

10. The method of claim 9, wherein introducing comprises flowing the silylgermane gas and the hydrogen gas from the same container.

11. The method of claim 9, wherein introducing comprises flowing the silylgermane gas and the hydrogen gas from separate containers.

12. The method of claim 1, wherein introducing comprises flowing an inert gas as the diluent.

13. The method of claim 12, wherein introducing comprises flowing nitrogen gas as the diluent.

14. The method of claim 12, wherein introducing comprises selecting a partial pressure for silylgermane in the reaction chamber to correlate with a desired germanium concentration in the deposited epitaxial silicon germanium layer.

15. A method for depositing an epitaxial layer comprising:
providing a substrate into a reaction chamber;
placing the substrate on a susceptor in the reaction chamber;
providing a source of silylgermane gas in communication with the reaction chamber; and
providing a source of reducing gas in communication with the reaction chamber;
selecting a ratio of the silylgermane gas to the reducing gas to modulate a percentage of germanium desired for the epitaxial layer; and
introducing a mixture of the silylgermane gas and the reducing gas having the selected ratio to the reaction chamber in the absence of germanium sources other than silylgerman to form an epitaxial silicon germanium layer having the desired percentage of germanium, wherein the epitaxial silicon germanium layer has between 60 atomic % germanium and 85 atomic % germanium.

16. The method of claim 15, wherein the reducing gas comprises hydrogen gas.

17. The method of claim 16, wherein introducing the mixture comprises flowing the reducing gas stored with the silylgermane gas in the selected ratio.

18. The method of claim 16, wherein introducing the mixture comprises flowing the reducing gas stored separately from the silylgermane gas.

19. The method of claim 16, wherein introducing the mixture comprises providing the ratio of silylgermane gas to hydrogen gas of between about 1:1000 and 1:20.