Patent Grant
7648690
1. Field of the Invention
This application relates generally to the deposition of silicon-containing materials in semiconductor processing. More particularly, this application relates to the deposition of substitutionally-doped silicon-containing films by chemical vapor deposition using trisilane and a dopant source.
2. Description of the Related Art
The electrical properties of semiconductors such as silicon (Si), germanium (Ge) and alloys thereof (SiGe) are influenced by the degree to which the materials are strained. For example, silicon exhibits enhanced electron mobility under tensile strain, and silicon-germanium (SiGe) exhibits enhanced hole mobility under compressive strain. Methods of enhancing the performance of semiconductors are of considerable interest and have potential applications in a variety of semiconductor processing applications. As is well known, semiconductor processing is most commonly employed for the fabrication of integrated circuits, which entails particularly stringent quality demands, but such processing is also employed in a variety of other fields. For example, semiconductor processing techniques are often employed in the fabrication of flat panel displays using a wide variety of technologies and in the fabrication of microelectromechanical systems (MEMS).
A number of approaches for inducing strain in Si- and Ge-containing materials have focused on exploiting the differences in the lattice constants between various crystalline materials, e.g., Ge (5.65 Å), Si (5.431 Å) and carbon (3.567 Å for diamond). In one approach, thin layers of a particular crystalline material are deposited onto a different crystalline material in such a way that the deposited layer adopts the lattice constant of the underlying single crystal material. For example, strained SiGe layers may be formed by heteroepitaxial deposition onto single crystal Si substrates. Because the Ge atoms are slightly larger than the Si atoms, the deposited heteroepitaxial SiGe follows the smaller lattice constant of the Si beneath it and thus is compressively strained to a degree that varies as a function of the Ge content. Typically, the band gap decreases monotonically from 1.12 eV for pure Si to 0.67 eV for pure Ge as the Ge content in the SiGe increases. In another approach, tensile strain is introduced into a thin single crystalline silicon layer by heteroepitaxially depositing the silicon layer onto a strain-relaxed SiGe layer. In this example, the heteroepitaxially deposited silicon is strained because its lattice constant follows the larger lattice constant of the relaxed SiGe beneath it. The tensile strained heteroepitaxially deposited silicon typically exhibits increased electron mobility. In these approaches, the strain is developed at the substrate level before the device (e.g., a transistor) is fabricated.
Strain may be introduced into single crystalline Si-containing materials by substitutional doping, e.g., where the dopants replace Si in the lattice structure. For example, substitution of germanium atoms for some of the silicon atoms in the lattice structure of single crystalline silicon produces a compressive strain in the resulting substitutionally doped single crystalline silicon material because the germanium atoms are larger than the silicon atoms that they replace. A tensile strain may be introduced into single crystalline silicon by substitutional doping with carbon, because carbon atoms are smaller than the silicon atoms that they replace. See, e.g., Judy L. Hoyt, “Substitutional Carbon Incorporation and Electronic Characterization of Si1-yCy/Si and Si1-x-yGexCy/Si Heterojunctions,” Chapter 3 in “Silicon-Germanium Carbon Alloy,” Taylor and Francis, NY, pp. 59-89, 2002, the disclosure of which is incorporated herein by reference.
In situ doping is often preferred over ex situ doping followed by annealing to incorporate the dopant into the lattice structure because the annealing may undesirably consume thermal budget. However, in practice in situ substitutional carbon doping is complicated by the tendency for the dopant to incorporate non-substitutionally during deposition, e.g., interstitially in domains or clusters within the silicon, rather than by substituting for silicon atoms in the lattice structure. See, e.g., the aforementioned article by Hoyt. Non-substitutional doping also complicates substitutional doping using other material systems, e.g., carbon doping of SiGe, doping of Si and SiGe with electrically active dopants, etc. As illustrated in FIG. 3.10 at page 73 of the aforementioned article by Hoyt, prior deposition methods have been used to make crystalline silicon having an in situ doped substitutional carbon content of up to 2.3 atomic %, which corresponds to a lattice spacing of over 5.4 Å and a tensile stress of less than 1.0 GPa. However, prior deposition methods are not known to have been successful for depositing single crystal silicon having an in situ doped substitutional carbon content of greater than 2.3 atomic %.
Thus, there is a need for improved methods to accomplish in situ substitutional doping of Si-containing materials. Desirably, such improved methods would be capable of achieving commercially significant levels of substitutional doping without unduly sacrificing deposition speed, selectivity, and/or the quality (e.g., crystal quality) of the deposited materials.
Deposition methods have now been developed that utilize a silicon source and a carbon source to deposit carbon-doped Si-containing films. Such deposition methods are capable of producing a variety of Si-containing single crystal films that are substitutionally doped with carbon to various levels, including levels that are significantly higher than those achieved using prior methods. For example, preferred deposition methods using trisilane as a silicon source can be used to deposit a variety of carbon-doped single crystal Si films having a range of substitutional carbon levels, including levels of greater than 2.3 atomic %. Other carbon-doped single crystal films, such as phosphorous- and arsenic-doped Si:C, may also be deposited by the methods described herein.
An embodiment provides a doped single crystalline silicon film comprising substitutional carbon, the single crystalline silicon film having a lattice spacing of 5.38 Å or less.
Another embodiment provides a single crystalline silicon film comprising 2.4 atomic % or greater substitutional carbon, as determined by x-ray diffraction and Vegard's Law. In preferred embodiments, the single crystalline silicon film comprises less than about 0.25 atomic % non-substitutional carbon, more preferably less than about 0.15 atomic % non-substitutional carbon.
Another embodiment provides a method for depositing a single crystalline silicon film, comprising:
Another embodiment provides an integrated circuit comprising a first single crystalline Si-containing region and a second single crystalline Si-containing region, at least one of the first single crystalline Si-containing region and the second single crystalline Si-containing region comprising an amount of substitutional carbon effective to exert a tensile stress on a third single crystalline Si-containing region positioned between the first single crystalline Si-containing region and the second single crystalline Si-containing region, the third single crystalline Si-containing region exhibiting an increase in carrier mobility of at least about 10% as compared to a comparable unstressed region.
These and other embodiments are described in greater detail below.
Deposition methods have now been developed that are useful for making a variety of substitutionally doped single crystalline Si-containing materials. For example, it has been found that crystalline Si may be in situ doped to contain relatively high levels of substitutional carbon by carrying out the deposition at a relatively high rate using trisilane as a silicon source and a carbon-containing gas as a carbon source. In preferred embodiments, the resulting carbon-doped Si-containing material is substitutionally doped to a significant degree. For example, the degree of substitutional carbon doping may be about 70% or greater, preferably about 80% or greater, more preferably about 90% or greater, expressed as the weight percentage of substitutional carbon dopant based on total amount of carbon dopant (substitutional and non-substitutional) in the silicon. The deposition of carbon-doped layers in accordance with this aspect can be conducted with or without an etchant gas, selectively or non-selectively, as described in greater detail below.
The term “Si-containing material” and similar terms are used herein to refer to a broad variety of silicon-containing materials including without limitation Si (including crystalline silicon), Si:C (e.g., carbon-doped crystalline Si), SiGe and SiGeC (e.g., carbon-doped crystalline SiGe). As used herein, “carbon-doped Si”, “Si:C”, “SiGe”, “carbon-doped SiGe”, “SiGe:C” and similar terms refer to materials that contain the indicated chemical elements in various proportions and, optionally, minor amounts of other elements. For example, “SiGe” is a material that comprises silicon, germanium and, optionally, other elements, e.g., dopants such as carbon and electrically active dopants. Thus, carbon-doped Si may be referred to herein as Si:C or vice versa. Terms such as “Si:C”, “SiGe”, and “SiGe:C” are not stoichiometric chemical formulas per se and thus are not limited to materials that contain particular ratios of the indicated elements. The percentage of a dopant (such as carbon, germanium or electrically active dopant) in a Si-containing film is expressed herein in atomic percent on a whole film basis, unless otherwise stated.
The amount of carbon substitutionally doped into a Si-containing material may be determined by measuring the perpendicular lattice spacing of the doped Si-containing material by x-ray diffraction, then applying Vegard's law (linear interpolation between single crystal Si and single crystal carbon) in a manner known to those skilled in the art. For example, the amount of carbon substitutionally doped into Si may be determined by measuring the perpendicular lattice spacing of the doped Si by x-ray diffraction, then applying Vegard's law. Those skilled in the art are aware of Vegard's law and the relationships between substitutional carbon level, lattice spacing and strain. See, e.g., Judy L. Hoyt, “Substitutional Carbon Incorporation and Electronic Characterization of Si1-yCy/Si and Si1-x-yGexCy/Si Heterojunctions,” Chapter 3 in “Silicon-Germanium Carbon Alloy,” Taylor and Francis, NY, pp. 59-89, 2002. As illustrated in FIG. 3.10 at page 73 of the aforementioned article by Hoyt, the total carbon content in the doped silicon may be determined by SIMS, and the non-substitutional carbon content may be determined by subtracting the substitutional carbon content from the total carbon content. The amount of other elements substitutionally doped into other Si-containing materials may be determined in a similar manner.
Various embodiments provide methods for depositing carbon-doped Si-containing materials (such as carbon-doped single crystalline Si) using a silicon source that comprises trisilane, a carbon source and, optionally, source(s) of other elements such as electrical active dopant(s). Under the CVD conditions taught herein, the delivery of trisilane and a carbon source to the surface of a substrate preferably results in the formation of an epitaxial carbon-doped Si-containing film on the surface of the substrate. In certain selective deposition embodiments described in greater detail below, an etchant gas such as chlorine gas (Cl2) is delivered to the substrate in conjunction with the trisilane and carbon source, and the Si-containing film is deposited selectively over single crystal substrates or single crystal regions of mixed substrates. Methods employing relatively high deposition rates are preferred, and in preferred embodiments such methods have been found to result in the deposition of in situ doped crystalline Si-containing materials containing relatively high levels of substitutional carbon.
“Substrate,” as that term is used herein, refers either to the workpiece upon which deposition is desired, or the surface exposed to the deposition gas(es). For example, the substrate may be a single crystal silicon wafer, or may be a semiconductor-on-insulator (SOI) substrate, or may be an epitaxial Si, SiGe or Ill-V material deposited upon such wafers. Workpieces are not limited to wafers, but also include glass, plastic, or any other substrate employed in semiconductor processing. The term “mixed substrate” is known to those skilled in the art, see U.S. Pat. No. 6,900,115 (issued May 31, 2005), entitled “Deposition Over Mixed Substrates,” which is hereby incorporated herein by reference in its entirety and particularly for the purpose of describing mixed substrates. As discussed in U.S. Pat. No. 6,900,115, a mixed substrate is a substrate that has two or more different types of surfaces. For example, a mixed substrate may comprise a first surface having a first surface morphology and a second surface having a second surface morphology. In certain embodiments, carbon-doped Si-containing layers are selectively formed over single crystal semiconductor materials while minimizing and more preferably avoiding deposition over adjacent dielectrics. Examples of dielectric materials include silicon dioxide (including low dielectric constant forms such as carbon-doped and fluorine-doped oxides of silicon), silicon nitride, metal oxide and metal silicate. The terms “epitaxial”, “epitaxially” “heteroepitaxial”, “heteroepitaxially” and similar terms are used herein to refer to the deposition of a crystalline Si-containing material onto a crystalline substrate in such a way that the deposited layer adopts or follows the lattice constant of the substrate. Epitaxial deposition may be heteroepitaxial when the composition of the deposited layer is different from that of the substrate.
Even if the materials are made from the same element, the surfaces can be different if the morphologies (crystallinity) of the surfaces are different. The processes described herein are useful for depositing Si-containing films on a variety of substrates, but are particularly useful for mixed substrates having mixed surface morphologies. Such a mixed substrate comprises a first surface having a first surface morphology and a second surface having a second surface morphology. In this context, “surface morphology” refers to the crystalline structure of the substrate surface. Amorphous and crystalline are examples of different morphologies. Polycrystalline morphology is a crystalline structure that consists of a disorderly arrangement of orderly crystals and thus has an intermediate degree of order. The atoms in a polycrystalline material are ordered within each of the crystals, but the crystals themselves lack long range order with respect to one another. Single crystal morphology is a crystalline structure that has a high degree of long range order. Epitaxial films are characterized by a crystal structure and orientation that is identical to the substrate upon which they are grown, typically single crystal. The atoms in these materials are arranged in a lattice-like structure that persists over relatively long distances (on an atomic scale). Amorphous morphology is a non-crystalline structure having a low degree of order because the atoms lack a definite periodic arrangement. Other morphologies include microcrystalline and mixtures of amorphous and crystalline material. As used herein, “single-crystal” or “epitaxial” is used to describe a predominantly large crystal structure that may have a tolerable number of faults therein, as is commonly employed for transistor fabrication. The skilled artisan will appreciate that crystallinity of a layer generally falls along a continuum from amorphous to polycrystalline to single-crystal; the skilled artisan can readily determine when a crystal structure can be considered single-crystal or epitaxial, despite low density faults. Specific examples of mixed substrates include without limitation single crystal/polycrystalline, single crystal/amorphous, epitaxial/polycrystalline, epitaxial/amorphous, single crystal/dielectric, epitaxial/dielectric, conductor/dielectric, and semiconductor/dielectric. The term “mixed substrate” includes substrates having more than two different types of surfaces, and thus the skilled artisan will understand that methods described herein for depositing Si-containing films onto mixed substrates having two types of surfaces may also be applied to mixed substrates having three or more different types of surfaces.
Carbon-doped Si-containing Films and Methods
An embodiment provides a method for depositing a single crystalline silicon film, comprising: providing a substrate disposed within a CVD reactor; introducing trisilane and a carbon source to the reactor under chemical vapor deposition conditions; and depositing a single crystalline silicon film onto the substrate. The deposition is preferably carried out at a deposition rate of at least about 5 nm per minute, more preferably at least about 10 nm per minute, even more preferably at least about 20 nm per minute. Preferably, the resulting single crystalline silicon film comprises at least about 1.0 atomic % substitutional carbon, more preferably about 1.5 atomic % or greater substitutional carbon, even more preferably 2.4 atomic % or greater substitutional carbon, as determined by x-ray diffraction and Vegard's Law.
Deposition may be suitably conducted according to the various CVD methods known to those skilled in the art, but the greatest benefits are obtained when deposition is conducted according to the CVD methods taught herein. The disclosed methods may be suitably practiced by employing CVD, including plasma-enhanced chemical vapor deposition (PECVD) or thermal CVD, utilizing trisilane vapor and a carbon source to deposit a single crystalline Si-containing film onto a substrate within a CVD chamber. In some embodiments, the Si-containing film is a carbon-doped epitaxial Si film. In some embodiments, a gaseous chlorine-containing etchant (such as HCl or, more preferably, chlorine) is introduced to the chamber in conjunction with the trisilane and carbon source to thereby selectively deposit a single crystalline Si-containing film. In the following description, reference may be made to the use of trisilane and a carbon source to deposit a Si or Si-containing film. It will be recognized that those descriptions are also generally applicable to the deposition of other Si-containing films, e.g., the deposition of SiGe:C films (e.g., involving the use of a germanium source), to the deposition of electrically doped Si:C and SiGe:C films (e.g., involving the use of a dopant precursor for an electrical dopant) and to selective depositions (e.g., involving the use of an etchant source), unless otherwise stated. Thermal CVD is preferred, as deposition can be achieved effectively without the risk of damage to substrates and equipment that attends plasma processing.
Trisilane and the carbon source (and, optionally, an etchant gas and/or an electrical dopant precursor, in certain embodiments) are preferably introduced to the chamber in the form of separate gases or by intermixing to form a feed gas. The intermixing to form the feed gas may take place in the chamber or prior to introduction of the feed gas to the chamber. The total pressure in the CVD chamber is preferably in the range of about 0.001 Torr to about 1000 Torr, more preferably in the range of about 0.1 Torr to about 350 Torr, most preferably in the range of about 0.25 Torr to about 100 Torr. Experiments were conducted with pressures ranging from 0.25 Torr to 100 Torr. In some embodiments, the chemical vapor deposition conditions comprise a chamber pressure of at least about 20 Torr, preferably a chamber pressure in the range of about 20 Torr to about 200 Torr. Chamber pressures of about at least about 500 mTorr were suitable in single wafer, single pass, laminar horizontal flow reactor in which the experiments were conducted, as described below. The chamber pressure may be referred to herein as a deposition pressure. The partial pressure of trisilane is preferably in the range of about 0.0001% to about 100% of the total pressure, more preferably about 0.001% to about 50% of the total pressure. The feed gas can also include a gas or gases other than trisilane and the carbon source, such as other silicon sources, etchant sources, dopant precursor(s) and/or inert carrier gases, but preferably trisilane is the sole source of silicon. The term “dopant precursor(s)” is used herein to refer in a general way to various materials that are precursors to various elements (e.g., carbon, germanium, boron, gallium, indium, arsenic, phosphorous, and/or antimony) that may be incorporated into the resulting deposited film in relatively minor amounts. It will be recognized that silicon sources may also be considered dopant precursors for the deposition of SiGe films that contain relatively minor amounts of silicon. Examples of suitable carrier gases for the methods described herein include He, Ar, H2, and N2. In certain embodiments, the carrier gas is a non-hydrogen carrier such as He, Ar and/or N2 as described in greater detail below. Preferably, trisilane is introduced to the chamber by way of a vaporizer such as a bubbler used with a carrier gas to entrain trisilane vapor, more preferably by way of a delivery system comprising a bubbler and a gas concentration sensor that measures the amount of trisilane in the carrier gas flowing from the bubbler. Such sensors are commercially available, e.g., Piezocon® gas concentration sensors from Lorex Industries, Poughkeepsie, N.Y., U.S.A.
Examples of suitable carbon sources that may be included in the feed gas include without limitation silylalkanes such as monosilylmethane, disilylmethane, trisilylmethane and tetrasilylmethane, and/or alkylsilanes such as monomethyl silane (MMS), and dimethyl silane. In some embodiments, a carbon source comprises H3Si—CH2—SiH2—CH3 (1,3-disilabutane). The feed gas may also contain other materials known by those skilled in the art to be useful for doping or alloying Si-containing films, as desired, such as a supplemental silicon source, germanium source, boron source, gallium source, indium source, arsenic source, phosphorous source, and/or antimony source. Specific examples of such sources include: silane, disilane and tetrasilane as supplemental silicon sources; germane, digermane and trigermane as germanium sources; monosilylmethane, disilylmethane, trisilylmethane, tetrasilylmethane, monomethyl silane (MMS), and dimethyl silane as sources of both carbon and silicon; and various dopant precursors as sources of electrical dopants (both n-type and p-type) such as antimony, arsenic, boron, gallium, indium and phosphorous. Chlorosilylmethanes of the general formula (SiH3-zClz)xCH4-x-yCly, where x is an integer in the range of 1 to 4 and where y and z are each independently zero or an integer in the range of 1 to 3, with the provisos that x+y≦4 and at least one of y and z is not zero, have been found to be particularly useful as sources of carbon, silicon and chlorine. Alkylhalosilanes of the general formula XaSiHb(CnH2n+1)4-a-b are also particularly useful as sources of carbon, silicon and chlorine, where X is a halogen (e.g., F, Cl, Br); n is 1 or 2; a is 1 or 2; b is 0, 1 or 2; and the sum of a and b is less than 4. Methyldichlorosilane (Cl2SiH(CH3)) is an example of an alkylhalosilane of the formula XaSiHb(CnH2n+1)4-a-b.
Incorporation of electrically active dopants into Si-containing films by CVD using trisilane is preferably accomplished by in situ doping using dopant sources or dopant precursors. Preferred precursors for electrical dopants are dopant hydrides, including p-type dopant precursors such as diborane, deuterated diborane, and n-type dopant precursors such as phosphine, arsenic vapor, and arsine. Silylphosphines, e.g., (H3Si)3-xPRx, and silylarsines, e.g., (H3Si)3-xAsRx, where x=0-2 and Rx=H and/or deuterium (D), are alternative precursors for phosphorous and arsenic dopants. SbH3 and trimethylindium are alternative sources of antimony and indium, respectively. Such dopant precursors are useful for the preparation of preferred films as described below, preferably boron-, phosphorous-, antimony-, indium-, and arsenic-doped silicon, Si:C, SiGe and SiGeC films and alloys.
A suitable manifold may be used to supply feed gas(es) to the CVD chamber. The CVD chamber is preferably in a single wafer reactor, e.g., a single wafer, horizontal gas flow CVD chamber as described in the illustrated embodiments. Most preferably, the CVD chamber is in a single-wafer, single pass, laminar horizontal gas flow reactor, preferably radiantly heated. Suitable reactors of this type are commercially available, and preferred models include the Epsilon™ series of single wafer reactors commercially available from ASM America, Inc. of Phoenix, Ariz. While the methods described herein can also be employed in alternative reactors, such as a showerhead arrangement, benefits in increased uniformity and deposition rates have been found particularly effective in the horizontal, single-pass laminar gas flow arrangement of the Epsilon™ chambers, employing a rotating substrate, particularly with low process gas residence times. CVD may be conducted by introducing plasma products (in situ or downstream of a remote plasma generator) to the chamber, but as noted above, thermal CVD is preferred.
The amount of dopant precursor in the feed gas may be adjusted to provide the desired level of dopant in the Si-containing film. Preferred concentrations of dopant precursor in the feed gas are in the range of about 1 part per billion (ppb) to about 20% by weight based on the total weight of reactive gas (excluding inert carrier and diluent gases). For electrical dopants, preferred concentrations of dopant precursor (e.g., pure phosphine or equivalent diluted phosphine, arsine or diborane) in the feed gas are preferably between about 0.1 standard cubic centimeters per minute (sccm) to about 5 sccm, although higher or lower amounts are sometimes preferred in order to achieve the desired property in the resulting film. In the preferred Epsilon™ series of single wafer reactors, dilute mixtures of the dopant precursor in a carrier gas can be delivered to the reactor via a mass flow controller with set points ranging from about 10 sccm to about 1000 sccm, depending on desired dopant concentration and dopant gas concentration. Dilution of dopant gases can lead to factors of 10−7 to 10−2 to arrive at equivalent pure dopant flow rates. Typically commercially available dopant sources are dopant hydrides diluted in H2, e.g., 1% arsine or 1% phosphine in H2. However, as described below with respect to
The relative amounts of the various feed gas components may be varied over a broad range depending on the composition desired for the resulting Si-containing film and the deposition conditions employed (e.g., temperature, pressure, deposition rate, etc.), and may be determined by routine experimentation in view of the guidance provided herein. The feed gas components may be intermixed and then delivered to the chamber or substrate, or the feed gas may be formed by mixing the components at or near the substrate, e.g., by supplying the feed gas components to the CVD chamber separately.
Thermal CVD is preferably conducted at a substrate temperature that is effective to deposit a crystalline Si-containing film over the substrate. Preferably, thermal CVD is conducted at a temperature in the range of about 350° C. to about 900° C., more preferably about 500° C. to about 800° C. In an embodiment, the chemical vapor deposition conditions comprise a temperature that is at about a transition temperature between substantially mass-transport controlled deposition conditions and substantially kinetically controlled deposition conditions for trisilane. Such trisilane deposition conditions are described in U.S. Pat. No. 6,821,825, which is hereby incorporated by reference and particularly for the purpose of describing trisilane deposition conditions. PECVD is preferably conducted at a temperature in the range of about 300° C. to about 700° C. Those skilled in the art can adjust these temperature ranges to take into account the realities of actual manufacturing, e.g., preservation of thermal budget, deposition rate, different sizes of chambers, including single wafer and batch reactors, preferred total pressures and partial pressures etc. In general, higher partial pressures entail lower temperatures for a given desired result, whether it be deposition rate, layer quality or a combination of the two. The substrate can be heated by a variety of methods known in the art, e.g., resistive heating and lamp heating.
Various deposition parameters have been found to affect the incorporation of substitutional carbon into Si-containing films, including: the ratio of trisilane to other silicon sources; the ratio of carbon source flow rate to trisilane flow rate; the carrier gas flow rate; the deposition pressure; the deposition temperature; and the deposition rate. Surprisingly, it has been found that certain combinations of these parameters are particularly advantageous for achieving relatively high levels of substitutional carbon incorporation into Si-containing films. In particular, the following combinations are preferred:
In an embodiment, each of the aforementioned carbon-doped single crystalline silicon films further comprises an electrical active dopant, e.g., a dopant selected from the group consisting of phosphorous and arsenic, that is electrically active (substitutionally incorporated) as deposited. In various embodiments, the films contain an amount of the electrically active dopant that is effective to reduce resistivity, e.g., to provide a Si:C film having a resistivity of about 1.0 mΩ·cm or less, preferably about 0.7 mΩ·cm or less. In another embodiment, each of the aforementioned single crystalline silicon films comprises less than about 0.3 atomic % non-substitutional carbon, preferably less than about 0.25 atomic % non-substitutional carbon, more preferably less than about 0.20 atomic % non-substitutional carbon, even more preferably less than about 0.15 atomic % non-substitutional carbon.
Thus,
Although deposition pressure has a relatively modest effect on growth rate, it has been found to substantially affect the crystal quality of the deposited Si:C films. For example, in one set of experiments, a series of epitaxial Si:C films were deposited using trisilane and MMS at a deposition pressure of 15 Torr and a deposition temperature of 550° C. in an Epsilon™ single wafer reactor. At a MMS flow rate of 70 sccm, a hydrogen carrier gas flow rate of 20 slm, and a deposition time of 15 minutes, an epitaxial Si:C film having a substitutional carbon content of 1.92 atomic % and a thickness of 410 Å was deposited. The epitaxial quality of the film was high and essentially all of the carbon was substitutional, as indicated by x-ray diffraction. However, increasing the film thickness and/or carbon content was found to result in lower epitaxial quality for the resulting Si:C film. For example, a second deposition conducted under essentially the same deposition conditions (except for a deposition time of 20 minutes) resulted in a thicker Si:C film having a slightly higher carbon content (1.96 atomic %), but the epitaxial quality of the second film was lower than the first, with x-ray diffraction indicating lower crystallinity. Thus, under these conditions (including a deposition pressure of 15 Torr), increasing the thickness and carbon content of a Si:C film resulted in a decrease in epitaxial film quality. However, by using a higher deposition pressure, it was found that film thickness and/or carbon content could be increased while maintaining high epitaxial film quality. For example, a third Si:C film was deposited under essentially the same conditions as the first film, except that the deposition pressure was higher (40 Torr) and the MMS flow rate was lower (46 sccm). The resulting film had a substitutional carbon content of 1.99 atomic % and a thickness of 630 Å. Despite the lower MMS flow rate, the substitutional carbon content of the third film was slightly higher than the first film, and the growth rate was higher (increased from about 27 nm/min to about 32 nm/min). In addition, despite the increase in both thickness and carbon level, the epitaxial quality of the third film was comparable to the first, as determined by x-ray diffraction. As another example, a fourth Si:C film was deposited under essentially the same conditions as the first and third films, except that the deposition pressure was higher (90 Torr) and the MMS flow rate was lower (36 sccm). The resulting film had a substitutional carbon content of 2.27 atomic % and a thickness of 385 Å. Despite the lower MMS flow rate, the substitutional carbon content of the third film was significantly higher than both the first and third films. In addition, the epitaxial quality of the fourth film was comparable to both the first and third films, as determined by x-ray diffraction
For trisilane depositions conducted in single wafer reactors such as the preferred Epsilon™ series reactors, trisilane flow rates are suitably in the range of about 5 mg/min (milligrams per minute) to about 2,000 mg/min, preferably in the range of about 50 mg/min to about 500 mg/min, more preferably about 100 mg/min to about 300 mg/min; carbon source (e.g., MMS) flow rates are preferably in the range of about 80 sccm to about 1000 sccm; ratios of carbon source flow rates to trisilane flow rates are preferably in the range of from about 0.5 standard cubic centimeters of carbon source per milligram trisilane (scc/mg) to about 8.0 scc/mg, more preferably from about 0.9 to about 3.0 scc/mg; carrier gas flow rates are preferably in the range of from about 1 slm to about 50 slm, more preferably about 10 slm to about 40 slm; deposition rates are preferably at least about 5 nm per minute, more preferably at least about 10 nm per minute; deposition pressures are preferably in the range of from about 1 Torr to about 200 Torr, more preferably about 10 Torr to about 100 Torr, even more preferably about 20 Torr to about 100 Torr; and deposition temperatures in the range of from about 450° C. to about 600° C., more preferably in the range of from about 500° C. to about 575° C. Those skilled in the art can adapt these conditions to various types of equipment and deposition configurations, using the guidance provided herein and routine experimentation. For example, the skilled artisan can readily adapt these conditions to deposit Ge-doped Si and carbon-doped SiGe.
As mentioned above, the aforementioned carbon-doped single crystalline Si-containing films may further comprise an electrically active dopant, e.g., a dopant selected from the group consisting of phosphorous and arsenic. In general, the presence of substitutional carbon results in scattering that tends to increase resistivity, as compared to an otherwise similar electrically-doped single crystalline Si-containing film that does not contain substitutional carbon. However, when deposited using trisilane as described herein, it has been found that such electrically-doped single crystalline Si-containing films may still have surprisingly low resistivities, despite the presence of the carbon. For example, when doped (preferably substitutionally doped) with an electrical dopant, the single crystalline Si-containing film comprising substitutional carbon may have a resistivity of about 1.0 mΩ·cm or less, preferably about 0.7 mΩ·cm or less. In experiments, a lattice spacing of about 5.323 Å (as measured by X-ray diffraction) has now been achieved for arsenic-doped Si:C deposited from trisilane, arsine and MMS. This lattice spacing of 5.323 Å corresponds to a substitutional carbon level of about 3.25%.
For example,
A single crystalline silicon film comprising relatively high levels of substitutional carbon as described herein (e.g., films comprising 2.4% or greater substitutional carbon) may exhibit various levels of tensile stress because the substitutional carbon atoms are smaller than the silicon atoms that they replace in the crystalline silicon lattice structure. In an embodiment, a single crystalline silicon film comprising 2.4% or greater substitutional carbon has a tensile stress of about 1.0 GPa or greater, e.g., about 1.5 GPa or greater, preferably about 1.7 GPa or greater, more preferably about 1.85 GPa or greater, even more preferably about 2.0 GPa or greater. The stress may be determined in any particular direction within the film. For example, for overlying silicon films comprising substitutional carbon that are deposited onto underlying crystalline silicon substrates, the overlying silicon film may exhibit a perpendicular stress (i.e., stress measured perpendicular to the film/substrate interface) that is different from the parallel stress (i.e., stress measured parallel to the film substrate interface). See, e.g., FIG. 3.1 at page 62 of the aforementioned article by Hoyt.
Stress may be introduced by heteroepitaxial deposition of the Si:C film onto a suitable substrate. For example, an arsenic-doped Si:C film having a substitutional carbon level of about 3.25 atomic % (lattice spacing of 5.323 Å) may be deposited onto a single crystal silicon substrate. When constrained to such a template (having a lattice spacing of about 5.43 Å), the tensile stress in such a Si:C film amounts to 2.06 GPa. The stress may be varied by appropriate selection of the substrate and the amount of substitutional carbon in the Si:C film. In various embodiments, the stress produced in a heteroepitaxially deposited Si:C film is preferably between 1 GPa and 3 GPa. When the Si:C is deposited to less than the critical thickness of the material, the deposited layer remains tensile stressed. In an embodiment, an electrically doped Si:C film is configured to exert a strain on an adjacent layer. For example, a compressive strain may be exerted on a silicon film that is deposited onto an electrically doped relaxed Si:C layer. In an embodiment, an electrically doped Si:C film formed in a recessed source/drain region exerts a tensile strain on a silicon channel formed between the source and drain, as described in greater detail below. Such configurations may be used in various applications, e.g., to improve electron mobility for NMOS devices.
In some embodiments, the thickness of a single crystalline silicon film comprising a strain-modifying amount of a substitutional dopant such as carbon as described herein is preferably less than a critical film thickness. Those skilled in the art understand that a critical film thickness is a film thickness at which a strained film relaxes under a particular set of conditions. As the concentration of substitutional dopant increases, the critical thickness generally decreases. Films having a thickness less than the critical thickness typically remain strained under those conditions. For example, a single crystalline silicon film comprising about 1.8 atomic % substitutional carbon may have a critical thickness of about 200 nm at 550° C., whereas an otherwise similar film comprising 3.5 atomic % substitutional carbon may have a critical thickness of about 25-30 nm at the same temperature. Films having a thickness that is less than a critical thickness for that film will tend to remain strained unless or until sufficiently perturbed (e.g., exposed to sufficient heat to cause relaxation).
As is known in the art, the lattice constant for single crystal silicon is about 5.431 Å, whereas single crystal germanium has a lattice constant of 5.657 due to the larger size of the germanium atoms. The deviation from silicon's natural lattice constant resulting from substitutional germanium incorporation introduces strain that advantageously improves electrical carrier mobility in semiconductors, improving device efficiency. When the SiGe is deposited to less than the critical thickness of the material, the deposited layer remains compressively strained and hole mobility is improved for PMOS devices. In such a case, the deposited SiGe layer can be selectively formed, e.g., over an entire active area and can define the channel, or it can act as a relaxed template for forming a compressively strained layer thereover, which can then itself serve as a channel region.
In the embodiments of FIGS. 8-13(described below), however, the Si:C layer is selectively formed in recessed source/drain regions 20, and is preferably deposited under conditions (thickness, temperature) that maintain stress. The smaller lattice constant of the Si:C material filling the S/D recesses exerts tensile strain on the channel region 22 therebetween. Preferably a dopant hydride is added to the process flow, in addition to trisilane, an etchant and a carbon source. Preferably an n-type dopant, and more preferably phosphine or arsine, is employed. A Si:C film comprising substitutional carbon may also be formed in source/drain regions by a blanket deposition and etching sequence, in a manner similar to that illustrated in
The processes described herein are useful for depositing Si-containing films on a variety of substrates, but are particularly useful for depositing Si-containing films over mixed substrates having mixed surface morphologies. As noted above, the term “mixed substrate” is known to those skilled in the art, see U.S. Pat. No. 6,900,115.
An embodiment provides a method for selectively depositing a carbon-doped single crystalline Si-containing film onto the single crystal region(s) of a mixed substrate. In addition to the uniformity and high quality films obtained by use of trisilane, as disclosed, e.g., in U.S. Pat. No. 6,821,825, it has been found that excellent selectivity can be obtained by the use of trisilane in combination with an etchant, e.g., a chlorine-containing etchant such as HCl, hexachlorodisilane (Si2Cl6) or chlorine gas (Cl2). Experiments have shown that selectivity can be 100% (i.e., with zero deposition on surrounding insulators such as silicon oxide and silicon nitride). HCl may be provided as an etchant to selective silicon-based deposition processes, where the etch effects upon slow-nucleating deposition on amorphous (typically insulating) surfaces is greater than the etch effects on exposed semiconductor surfaces. Chlorine is preferred as HCl is notoriously difficult to purify and typical commercial sources of HCl introduce excessive moisture into the deposition process. Such moisture can lower the conductivity of deposited films, and cause unacceptable levels of defects in epitaxial deposition. Accordingly, the use of a feed gas comprising trisilane, a carbon source and chlorine advantageously achieves high levels of selectivity without added etchants, and particularly without HCl.
Preferably, the feed gas is introduced to the chamber along with a hydrogen carrier gas, using a relatively high trisilane flow rate and a relatively low hydrogen flow rate, as compared to standard use of silane as the sole silicon precursor. The flow rate of the carbon source is selected to achieve the desired level of incorporation of substitutional carbon, as discussed in detail above for the incorporation of substitutional carbon with respect to
The elevated S/D structure 32 of
Advantageously, the selective nature of the trisilane/chlorine process obviates subsequent pattern and etch steps to remove excess deposition from over field regions. Even imperfect selectivity can advantageously permit use of a timed wet etch to remove unwanted deposition over insulating surfaces, rather than requiring an expensive mask step. Furthermore, superior film quality is obtained at relatively high deposition rates, improving throughput. For example, certain process embodiments may be used to selectively deposit boron-doped SiGeC using trisilane, methylsilane, B2H6, and chlorine to form, e.g., a base structure of a heterobipolar transistor (HBT).
A Si:C layer may be selectively formed in recessed source/drain regions 20 as discussed above. However, the Si:C layer may also be formed by a process that involves a blanket deposition of the Si:C layer, followed by etching so that single crystalline Si:C remains in the recessed source/drain regions 20. An embodiment of such a process is illustrated by the sequence shown in
The process illustrated in
Thus, an embodiment provides an integrated circuit comprising a first single crystalline Si-containing region and a second single crystalline Si-containing region, at least one (preferably both) of the first single crystalline Si-containing region and the second single crystalline Si-containing region comprising an amount of substitutional carbon effective to exert a tensile stress on a third single crystalline Si-containing region positioned between the first single crystalline Si-containing region and the second single crystalline Si-containing region, the third single crystalline Si-containing region exhibiting an increase in carrier mobility of at least about 10%, more preferably by at least about 20%, as compared to a comparable unstressed region. The integrated circuit may comprise one or more transistors in which the first single crystalline Si-containing region comprises a source, the second single crystalline Si-containing region comprises a drain, and the third single crystalline Si-containing region comprises a channel. An example of such a transistor is illustrated in
Deposition of Si-containing films using trisilane as described herein can offer significant advantages over the use of conventional silicon sources when conducted as described herein. For example, at a given deposition temperature, deposition of Si-containing films using trisilane preferably proceeds at a rate that is significantly faster than when silane is used instead of trisilane. A preferred embodiment provides a high rate deposition method in which trisilane is delivered to the substrate surface at a delivery rate of about 50-200 mg/min. Under thermal CVD conditions, preferably at a deposition temperature in the range of about 500° C. to about 800° C., practice of this embodiment results in relatively fast deposition of the Si-containing material (as compared to other silicon sources), often at a rate of about 50 Å per minute or higher, preferably about 100 Å per minute or higher, more preferably about 200 Å per minute or higher. Depositions using trisilane can be carried out at even higher deposition rates, e.g., about 400 Å per minute or higher, preferably about 800 Å per minute or higher, even more preferably about 1,000 Å per minute or higher. Preferably, a dopant hydride source is also delivered to the surface along with the trisilane and carbon source to improve surface quality and to provide in situ doping.
Preferred Si-containing films have a thickness that is highly uniform across the surface of the film. When deposition is conducted using trisilane as described herein, the percent thickness non-uniformity for the resulting Si-containing films is preferably about 2% or less. Depending on the mean thickness of the film, additional values for percent thickness non-uniformity may be preferred as shown in Table 1 below. Each value for % thickness non-uniformity shown in Table 1 is to be understood as if preceded by the word “about.”
In general, measurements of film thickness uniformity for a film deposited under a particular set of process conditions can be made by depositing the film on a uniform or mixed substrate having a diameter in the range of about 200 mm to about 300 mm. Film thickness uniformity is determined by making multiple-point thickness measurements along a randomly selected diameter (with no measurements being taken within a 3 mm exclusion zone at the wafer periphery), determining the mean thickness by averaging the various thickness measurements, and determining the root mean square (rms) variability. A preferred instrument for measuring film thickness utilizes an Optiprobe™ from Thermawave, and a preferred measurement method involves using such an instrument to measure the film thickness at 49 points along a randomly selected wafer diameter. In practice, thickness variability is typically obtained directly from the instrument following such a measurement, and thus need not be calculated manually. To enable comparisons, the results can be expressed as percent non-uniformity, calculated by dividing the rms thickness variability by the mean thickness and multiplying by 100 to express the result as a percentage. When measuring thickness uniformity of a film having a surface that is not accessible to such a measurement, e.g., a film onto which one or more additional layers have been applied, or a film contained within an integrated circuit, the film is cross sectioned and examined by electron microscopy. The film thickness is measured at the thinnest part of the cross sectioned film and at the thickest part, and the range in thickness measurements (e.g., ±6 Å) between these two points is then divided by the sum of the two measurements. This non-uniformity is expressed as a percentage herein.
In addition, the compositional uniformity of preferred crystalline Si-containing films that contain other elements (e.g., doped silicon, Si-containing Si:C and SiGe alloys, and doped Si-containing alloys) made in accordance with the methods described herein is materially improved as compared to corresponding films made without the use of trisilane. This invention is not bound by any theory of operation, but it is believed that the Si-containing films have a degree of compositional uniformity that is better than corresponding Si-containing films deposited using conventional precursors such as silane, dichlorosilane (DCS) or trichlorosilane (TCS). Furthermore, crystalline (e.g., single crystalline or polycrystalline) Si-containing alloys containing relatively high levels of non-silicon element(s) can be prepared by the methods described herein. For example, crystalline Si:C preferably contains between about 1 atomic % and about 3.5 atomic % of substitutional carbon.
In accordance with another aspect of the invention, for selective deposition embodiments a non-hydrogen carrier gas is preferably employed in combination with a substitutional dopant precursor (e.g., a carbon source), etchant gas and trisilane gas, as described above. Hydrogen gas (H2) is the most popular carrier gas employed in vapor deposition for semiconductor processing, and particularly in epitaxial deposition. There are several reasons for the popularity of H2. H2 can be provided with a high degree of purity. Furthermore, the thermal properties of hydrogen are such that it does not have as great a thermal effect on the wafer. Additionally, hydrogen has a tendency to act as a reducing agent, such that it combats the formation of native oxide that results from less than perfect sealing of the reaction chamber.
However, particular advantages have now been found from employing a non-hydrogen carrier gas in the substitutional dopant precursor/trisilane/chlorine deposition system described herein. Preferably helium (He), argon (Ar), neon (Ne), xenon (Xe) or nitrogen gas (N2), or a combination of such inert gases, is employed in place of hydrogen. In the illustrated embodiment, He is employed, as it has thermal behavior close to that of H2 and thus entails less tuning of the reactor for the adjustment from use of H2 carrier gas.
There are a number of possible reaction mechanisms in the trisilane/chlorine/hydrogen system described hereinabove, including the following:
Si(s)+Cl2(g)→SiCl2 (g) etching (1)
Si3H8 (g)→H3SiSiH: (g)+SiH4 (g) trisilane dissociation (2)
H3SiSiH: (g)→H2Si=SiH2 (g) (3)
SiH2 (g)+SiCl2 (s)→2 Si (s)+2 HCl (g) deposition (4)
Si (s)+2 HClSiCl2 (g)+H2 (g) balance of deposition and etching (5)
2 PH3 (g)→2 P (s)+3 H2 (g) doping (6)
PH3 (g)+6 Cl (s)→PCl3 (g)+3 HCl (g)+free surface sites (7)
Cl2 (g)+H2 (g)→2 HCl (g) (8)
Equation (1) represents an etching reaction in the system. In addition to providing etching (which is needed for selectivity to be maintained), equation (1) also produces a reactant for equation (5) that will tend to produce silicon deposition. Equation (5) represents a balance between reaction to the right (etching) and reaction to the left (deposition). Preferably conditions are such that etching dominates over insulating surfaces while deposition dominates over semiconductor windows. Without wanting to be limited by theory, it is desirable to provide a sufficient concentration of chlorine gas to produce etching for selectivity, while producing SiCl2 that provides for deposition.
However, when free H2 is present as a carrier gas (i.e., in large quantities), reaction (8) will take place, generating HCl. Increasing the concentration of HCl in the system drives both deposition/etch equations (4) and (5) in the direction of etching, thus driving down deposition rates for any given “tuned” process. A tuned process represents one in which the reactant concentrations have been tuned to achieve selective deposition.
Equation (7) illustrates yet another desirable reaction that is depressed by generation of HCl due to the presence of H2 carrier gas. Equation (7) illustrates gettering of chloride adsorbed on the wafer surface. Dopant hydrides, such as arsine, phosphine and diborane (phosphine shown) tend to react with surface chlorine atoms and form volatile byproduct(s), such that surface reaction sites are freed for depositions. As with equations (4) and (5), however, increasing the HCl concentration tends to depress the desirable gettering reaction by shifting the equilibrium for equation (7) to the left.
Accordingly, the use of a non-hydrogen carrier gas (which is generally the dominant gas in the system) will avoid the consumption of Cl2 by equation (8), thereby avoiding depressing the deposition reactions (4), (5) and the gettering reaction (7). The plots shown in
The flow through this MFC 112 merges with the main carrier gas through the main carrier gas MFC 114 and other reactants at the gas panel, upstream of the injection manifold 120 for the deposition chamber 122. A source of etchant gas 130 is also optionally provided for selective deposition processes, preferably Cl2 gas. In the illustrated embodiment, a carbon source 132 (illustrated as MMS) and a source for dopant hydride 134 (phosphine shown) are also provided.
As illustrated, the reactor system 100 also includes a central controller 150, electrically connected to the various controllable components of the system 100. The controller is programmed to provide gas flows, temperatures, pressures, etc., to practice the deposition processes as described herein upon a substrate housed within the reaction chamber 122. As will be appreciated by the skilled artisan, the controller 150 typically includes a memory and a microprocessor, and may be programmed by software, hardwired or a combination of the two, and the functionality of the controller may be distributed among processors located in different physical locations. Accordingly, the controller 150 can also represent a plurality of controllers distributed through the system 100.
Accordingly, the combination of carbon source/trisilane results in enhanced deposition rates for silicon-containing materials, particularly epitaxial layers. In one embodiment, the gas flow rates are selected, in combination with pressure and temperature, to achieve selective deposition of Si:C on/in semiconductor windows among insulating material.
In the illustrated embodiment, with the carbon source 132 in combination with trisilane and chlorine, selective deposition of high substitutional carbon content Si:C can be achieved, as disclosed hereinabove. In another embodiment, the dopant hydride source 134 is preferably also provided to produce in situ doped semiconductor layers with enhanced conductivity. Preferably, for Si:C epitaxy, the dopant hydride is arsine or phosphine, and the layer is n-type doped. More preferably, for selective deposition embodiments, the diluent inert gas for the dopant hydride is also a non-hydrogen inert gas. Thus, phosphine and MMS are preferably stored at their source containers 132, 134 in, e.g., helium. Typical dopant hydride concentrations are 0.1% to 5% in helium, more typically 0.5% to 1.0% in helium for arsine and phosphine. Typical carbon source concentrations are 5% to 50% in helium, more typically 10% to 30% in helium. For example, experiments are being conducted with 20% MMS in helium.
The foregoing discussion about the benefits of non-hydrogen inert carrier gases in combination with a carbon source, trisilane and chlorine gas is also applicable to other semiconductor compounds. For example, trisilane, germane, chlorine and a non-hydrogen carrier gas will obtain the same enhanced and selective deposition benefits for SiGe. For example, a p-type doped layer can be obtained with the addition of 1% diborane in helium.
An eight-inch unpatterned Si<100> wafer substrate was loaded into an Epsilon E2500™ reactor system. The substrate was then introduced into the reactor system at 900° C., at a hydrogen flow rate of 20 slm, and the substrate was allowed to stabilize for 1 minute. The hydrogen flow was then reduced to 2 slm as the temperature of the substrate was reduced to 550° C. The substrate was then allowed to stabilize for 10 seconds, after which time a flow of 50 mg/min of trisilane and 40 sccm of MMS was introduced for 7.5 minutes. A flow of 100 sccm phosphine (1% in H2) was simultaneously provided and the deposition was conducted at a deposition pressure of about 64 Torr. A continuous, uniform phosphorous-doped Si:C film having a thickness of about 210 nm (XRD) was deposited (deposition rate of about 28 nm/min) over the single crystal substrate. The substrate was then removed from the reactor and returned to the loadlock. The phosphorous-doped Si:C film deposited on the silicon wafer had excellent epitaxial quality, a resistivity of 0.8 mΩ·cm (center) and contained about 3.5 atomic % carbon.
A phosphorous-doped Si:C film was deposited in the manner described in Example 1 except that a patterned substrate having single crystal regions and insulator (oxide) regions was used. The phosphorous-doped Si:C film formed over both the single crystal and the insulator regions, and had substantially the same thickness (about 200 nm) over both.
All patents, patent applications and papers mentioned herein are hereby incorporated by reference in their entireties. It will be appreciated by those skilled in the art that various omissions, additions and modifications may be made to the processes described above without departing from the scope of the invention, and all such modifications and changes are intended to fall within the scope of the invention, as defined by the appended claims.
This application is a divisional of U.S. Non-Provisional Application No. 11/343,275, filed Jan. 30, 2006 now U.S. Pat. No. 7,438,760, which claims priority to U.S. Provisional Application No. 60/649,990, filed Feb. 4, 2005; U.S. Provisional Application No. 60/663,434, filed Mar. 18, 2005; and U.S. Provisional Application No. 60/668,420, filed Apr. 4, 2005; all of which are hereby incorporated by reference in their entireties. This application is related to, and incorporates by reference in their entireties, the following U.S. patent applications: U.S. patent application Ser. No. 11/343,264, entitled “SELECTIVE DEPOSITION OF SILICON-CONTAINING FILMS ; and U.S. patent application Ser. No. 11/343,244, entitled “METHODS OF MAKING ELECTRICALLY DOPED CRYSTALLINE SI-CONTAINING FILMS, both of which are filed on even date with the parent application.
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