Implantation at elevated temperatures for amorphization re-crystallization of Si1-xGex films on silicon substrates

[0002] This Application is related to (1) Method to form relaxed SiGe layer with high Ge content, Ser. No. 10/062,319, filed Jan. 31, 2002; (2) Method to form thick relaxed SiGe layer with trench structure, Ser. No. 10/062,336, filed Jan. 31, 2002; (3) Amorphization Re-crystallization of Si_1−xGe_xon Silicon film, Ser. No. 10/098,757, filed Mar. 13, 2002; (4) Method to form relaxed SiGe layer with high Ge content using implantation of molecular hydrogen, Ser. No. 10/099,374, filed Mar. 13, 2002 now U.S. Pat. No. 6,562,703; and (5), Amorphization Recrystallization of Si_1−xGe_xon Silicon Film; Ser. No. 10/124,853, filed Mar. 13, 2002.

[0003] This invention relates to devices for high speed CMOS integrated circuits, and specifically to fabrication of a SiGe film at an elevated temperature by providing a layer of tensile strained silicon on a relaxed Si_1−xGe_xlayer to speed switching speeds for nMOS and pMOS transistors.

[0004] There are many publications describing a thick layer of Si_1−xGe_xwith graded Ge composition (x) followed by a thick relaxed Si_1−xGe_xlayer of constant x capped by a thin silicon film under tensile strain, which is used for fabricating high drain drive current MOS transistors. Because of the lattice parameter mismatch between the Si_1−xGe_xlayers and the silicon substrate there is a high density of misfit dislocations at the SiGe/Si substrate interface, accompanied by numerous threading dislocations in the SiGe some of which propagate all the way to the surface. The total SiGe thickness is on the order of several microns and the density of threading dislocations at the surface is still on the order of 1·10⁵cm⁻². A partial list of the relevant publications is given in related Application 1. However, the very thick Si_1−xGe_xlayer, and the high defect density of this conventional Si_1−xGe_xprocess is not applicable for large-scale IC fabrication.

[0005] As is demonstrated in S. Mantl et al., Strain relaxation of epitaxial SiGe layer on Si(100) improved by hydrogen implantation, Nuclear Instruments and Methods in Physics Research B vol. 147, 29 (1999), and expanded upon in related Applications 1 and 2, strain relaxed high quality Si_1−xGe_xlayers on silicon can be obtained by hydrogen ion implantation and annealing. Hydrogen ion implantation forms a narrow defect band slightly below the SiGe/Si interface. During subsequent annealing hydrogen platelets and cavities form, nucleating misfit dislocations and giving rise to strong enhanced strain relaxation in the Si_1−xGe_xepilayer. Hydrogen ions may also terminate some threading dislocations, preventing them from propagating toward the Si_1−xGe_xsurface. Related Applications 1 and 2 describe methods to reduce defect density and fabricate high drive current MOS transistors on a relaxed Si_1−xGe_xfilm having thickness on the order of only 300 nm. However, the defect density of the Si_1−xGe_xfilm by these processes is still not suitable to very large-scale integrated circuit fabrication.

[0006] Related Application 3 describes a means to further reduce the defect density in Si_1−xGe_xfilms. In the method described in that Application, a buried amorphous region in the film is fabricated, e.g., with Si⁺ ion implantation, and then recrystallized through solid phase epitaxy (SPE) using as the seed the undamaged crystalline Si_1−xGe_xregion at the surface. However, the process window for making a buried amorphous region in SiGe may be rather narrow, because it has been consistently reported that SiGe is much more easily damaged by Si⁺ ion implantation than silicon, A. N. Larsen et al., MeV ion implantation induced damage in relaxedSi_1−xGe_x, J. Appl. Phys., vol. 81, 2208 (1997); T. E. Haynes, et al., Damage accumulation during ion implantation of unstrainedSi_1−xGe_xalloy layers, Appl. Phys. Lett., vol. 61, 61 (1992); and D. Y. C. Lie, et al., Damage and strain in epitaxial Ge_xSi_1−xfilms irradiated with Si, J. Appl. Phys. Vol. 74, 6039 (1993). The critical dose for amorphization, (φ_c) decreases with increasing Ge concentration. This holds true for both strained and relaxed SiGe. This effect is thought to be due to both an increase in the average energy density per ion deposited in the collision cascade and a stabilization of the damage through a reduction of defect mobility in SiGe, Lie et al. and Haynes et al. To overcome this problem, related Application 5 describes the use of a thin silicon cap layer which acts as a crystalline seed for solid phase epitaxial regrowth of the underlying amorphized SiGe film. Because the silicon cap will experience considerably less damage from the Si⁺ implant than the SiGe it should make a better template for the regrown crystal.

[0007] However, SPE of amorphized strained SiGe with more than 10% Ge has been observed to result in a heavily defected film, containing microtwins and stacking faults, which have been explained as a stress relief mechanism, D. C. Paine, et al., The growth of strained Si_1−xGe_xalloys on(001) silicon using solid phase epitaxy, J. Mater. Res., vol. 5, 1023 (1990), and C. Lee, et al., Kinetics of solid phase epitaxial regrowth in amorphizedSi_0.88Ge_0.12measured by time-resolved reflectivity, Appl. Phys. Lett., vol. 62, 501 (1993). Correspondingly, it has been reported that SPE of relaxed SiGe amorphized by Si⁺ ion implantation results in a much better crystal than SPE of strained SiGe, Q. Z. Hong, et al., Solid phase epitaxy of stresses and stress-relaxed Ge-Si alloys, J. Appl. Phys. Vol. 71, 1768 (1992). Furthermore, the SPE recrystallization rate of strained SiGe is slower than that of silicon while the rate for relaxed SiGe is higher, which is attributed to changes in the activation barrier for SPE, Hong et al.

[0008] There is also a strong dependence on the wafer temperature during ion implantation, T_I, with the damage decreasing at higher T_I, so φ_cwill depend on temperature, Haynes et al. This is thought to be due to the increased mobility at higher temperatures of the defects resulting from implantation, Haynes et al.; D. Y. C. Lie, et al., Dependence of damage and strain on the temperature of Si irradiation in epitaxial Ge_0.10Si_0.90films on Si(100), J. Appl. Phys. Vol. 77, 2329 (1995); and O. W. Holland, et al., Damage saturation during high-energy ion implantation of Si_1−xGe_x, Appl. Phys. Lett., vol. 61, 3148 (1992). This is reported to be a strong effect, occurring fairly abruptly, so that the same implant, e.g., 1·10¹⁵Si⁺ ions at 320 keV, will amorphize Si_0.9Ge_0.1at T_I=60° C., but barely damage the lattice at 100° C., Lie, et al., supra. Also, at elevated T_I, the damage may depend on dose rate as well as total dose, Haynes et al. Another effect reported to occur at elevated wafer temperatures is saturation of the damage during Si⁺ ion implantation, Holland et al. If Si⁺ ions are implanted into Si, SiGe, or Ge at T_Igreater than some critical value, T_c, the surface damage will not rise above a relatively low value no matter what the dose; i.e., it saturates. Meanwhile, as the dose is increased the end-of-range (EOR) damage grows until a buried amorphous region is produced. However, if T_Iis too high, it may not be possible to produce an amorphous region, regardless of dose, Haynes et al. If the implant is performed at T_Ibelow T_c, the damage in both the surface region and EOR will increase with dose. Consequently, there is expected to be an optimum temperature range for T_Iwhich allows fabrication of a buried amorphous region while preserving a crystalline surface layer. T_cis composition dependent: e.g. ˜24° C., 69° C., 133° C., and 114° C. for Si, 15% Ge, 50% Ge, and 100% Ge, at a 1.25 meV implant energy, respectively, Holland et al. The method of the invention described herein makes use of these temperature effects to preserve the crystal quality of the surface region during Si⁺ or Ge⁺ ion implantation of SiGe while producing a buried amorphous region. By so doing a better quality crystal can be fabricated after solid phase epitaxial regrowth.

[0009] A method of fabricating a Si_1−XGe_Xfilm on a silicon substrate includes preparing a silicon substrate; epitaxially depositing a Si_1−XGe_Xlayer on the silicon substrate forming a Si_1−XGe_X/Si interface there between; amorphizing the Si_1−XGe_Xlayer at a temperature greater than T_cto form an amorphous, SiGe layer; and annealing the structure at a temperature of between about 650° C. to 1100° C. for between about ten seconds and sixty minutes to recrystallize the SiGe layer.

[0010] It is an object of the invention to make use of temperature effects during amorphization to preserve the crystal quality of the surface region.

[0011] Another object of the invention is to produce a buried amorphous region by Si⁺ or Ge⁺ ion implantation into a SiGe layer at a temperature above T_c.

[0012] Another object of the invention is to provide a method to produce low defect density, 200 nm to 500 nm thick relaxed Si_1−xGe_xfilms with Ge content of up to 50% or more at the top surface for large-scale integrated circuit application.

[0013] A further object of the invention is to provide a better quality crystal after solid phase eptiaxial regrowth.

[0014] Another object of the invention is to provide a strained silicon layer on a relaxed Si_1−xGe_xlayer.

[0015] This summary and objectives of the invention are provided to enable quick comprehension of the nature of the invention. A more thorough understanding of the invention may be obtained by reference to the following detailed description of the preferred embodiment of the invention in connection with the drawings.

[0016] FIG. 1 depicts an as-grown film.

[0017] FIG. 2 depicts a cross-section of the film after hydrogen implantation before any annealing.

[0018] FIG. 3 depicts a cross-section of the film after relaxation annealing.

[0019] FIG. 4 depicts a cross-section of the film after Si⁺ or Ge⁺ ion implantation at an optimum wafer temperature above T_c.

[0020] FIG. 5 depicts a cross-section of the film after SPE recrystallization and growth of tensile-strained silicon cap.

[0021] FIG. 6 depicts an as-grown film fabricated by an alternate method of the invention.

[0022] FIG. 7 depicts a cross-section of the film after SPE recrystallization and growth of a second tensile-strained silicon cap according to the method of FIG. 6.

[0023] As explained above, SiGe is more easily damaged by ion implantation than is Si, making it difficult to produce a buried amorphous layer in SiGe. However, if the wafer temperature during implantation is above a critical temperature, T_c, the damage in the surface region saturates at a relatively low value, Holland et al. Therefore, by implanting Si⁺ or Ge⁺ ions above T_c, but not at too high a temperature, the crystallinity of the surface SiGe is more easily preserved and is able to form a template for solid phase epitaxy (SPE) of the amorphized SiGe layer beneath. The method of the invention includes implantation of Si⁺ or Ge⁺ ions at an optimum temperature above T_cto produce a buried amorphous layer in a Si_1−xGe_xfilm while preserving the crystallinity of the surface region. The Si_1−xGe_xfilm may or may not have a thin silicon cap. Furthermore, prior to Si⁺ implantation the Si_1−xGe_xfilm may be pseudomorphic to the silicon substrate or relaxed.

[0024] Referring now to FIG. 1, the method of the invention for elevated temperature defect reduction includes forming a structure 10, including preparation of a silicon substrate 12, having an as-grown Si_1−xGe_xpseudomorphic (strained) film 14 thereon. In this first embodiment of the method of the invention, no silicon cap is formed over the Si_1−xGe_xpseudomorphic film. Silicon substrate 12 is prepared by state-of-the-art techniques. Graded Si_1−xGe_xepitaxial layer 14 is grown to a thickness such that there is no relaxation in the Si_1−xGe_xlayer at the growth temperature; such a film may be thermodynamically metastable but still free of dislocations. The value of x at the bottom of the Si_1−xGe_xlayer, that is at the Si_1−xGe_x/Si interface, can be lower than 0.05 while at the top surface of the Si_1−xGe_xlayer it is between about 0.2 to 0.5 or greater. The Ge concentration may be increased linearly, stepwise, or in some other fashion with increasing Si_1−xGe_xthickness. This is suitable for a Si_1−xGe_xfilm thickness of between about 200 nm to 500 nm. Because the SiGe film is not relaxed the top surface, is free from defects. Alternatively, a Si_1−xGe_xepitaxial layer with constant value of x may be grown, but for a given value of x at the top surface a thinner film is required to avoid the nucleation of dislocations and resulting relaxation. If desired, a thin epitaxial silicon cap may be grown on top of the Si_1−xGe_xepitaxial layer, which variation of the method of the invention will be described later herein.

[0025] Referring now to FIG. 2, hydrogen ions, e.g., H+, on the order of 1·10¹⁶cm⁻²to 4·10¹⁶cm⁻²are implanted into the Si_1−xGe_xfilm at a proper ion energy, e.g., 30 keV to 80 keV, which provides a projected depth of between about 3 nm to 100 nm below than the Si_1−xGe_x/Si interface, forming a layer 16 having a high density of hydrogen. Alternatively, singly ionized molecular hydrogen, e.g., H₂+, with half the dose but twice the energy of H+ may be used, as described in related Application 4. Another alternative is to implant boron with the hydrogen, or to use helium ions. Another alternative is to perform no implantation, in which case, the following step is not required.

[0026] Referring to FIG. 3, the films may be annealed to relax the SiGe layer, forming a graded, relaxed SiGe layer 14a. The annealing temperature is between about 700° C. to 1100° C. The annealing time is between about 10 seconds to longer than 60 minutes. Rapid thermal annealing or furnace annealing may be used. During the anneal, hydrogen ions under the Si_1−xGe_x/Si interface form hydrogen platelets and cavities which enhance nucleation of misfit dislocations and so improve the efficiency of relaxation, forming a high defect SiGe/Si interface region 18. Alternatively, annealing may be delayed until after implantation of the amorphizing species, as described next.

[0027] Referring now to FIG. 4, a high dose, e.g., 5·10¹³cm⁻²to 10·10¹⁵cm⁻²of heavy ions, such as Si⁻, implanted at and energy of between about 30 keV to 500 keV, or Ge⁺ implanted at an energy of between about 60 keV to 1000 keV, are implanted into the Si_1−xGe_xepilayer to produce a buried amorphous film 20, which layer 20amay extend into silicon substrate 12, forming an amorphous layer near the SiGe/Si interface. During implantation the wafer is kept above a composition-dependent critical temperature, T_c, so that the implantation-induced damage in the surface region saturates at a relatively low value. However, the temperature should not be too high, or it may be difficult to amorphize any of the SiGe film. For example, for a 50% Ge film, where T_c˜133° C., an implant temperature of 155° C. with a Si⁺ dose of 4·10¹⁵cm⁻²has been reported to be effective, Holland et al. Ideally the entire Si_1−xGe_xlayer, except the top 10 nm to 50 nm, 22, which is only lightly damaged, will be converted to an amorphous structure. Therefore, multi-energy ion implantation is preferred for thicker Si_1−xGe_xfilms. The silicon cap, if present, will be more resistant to implant damage and should remain as a crystalline seed for subsequent SPE.

[0028] Next, the wafers undergo high temperature annealing, resulting in solid phase re-crystallization. The annealing temperature is between about 650° C. to 1100° C. The annealing time is between about 10 seconds to longer than 60 minutes. Rapid thermal annealing or furnace annealing may be used. The recrystallization will proceed from both the top high quality layer and from the Si_1−xGe_x/Si interface. However, the recrystallization from the lower interface will likely be heavily defected due to strain. Therefore, the amorphizing species must be implanted deeply enough so that these defects will be below the space charge region during transistor operation. Moreover, the rate of the recrystallization from the SiGe/Si interface may be slower, resulting in most of the SiGe film being recrystallized from the top layer, which is desirable.

[0029] Referring to FIG. 5, when the SiGe film re-crystallizes, layer 24, it is relaxed and defect free. A thin, e.g., 10 nm to 20 nm, tensile-strained pure silicon cap 28 may be epitaxially grown on top of layer 24, as required for production of high mobility MOS transistors.

[0030] Referring to FIG. 6, a structure 40 constructed according to an alternate method of the invention includes a silicon substrate 42 having a Si_1−xGe_xpseudomorphic film 44 thereon. Following epitaxial deposition of the Si_1−xGe_xpseudomorphic film, a silicon cap 46 is formed. The thickness of silicon cap 46 is much less than that of the SiGe; e.g., on the order of between about 10 nm to 20 nm. This silicon cap will be relaxed, having the same cubic structure and lattice constant as the silicon substrate. Cap 46 acts as a seed layer for SPE. However, during the annealing steps substantial amounts of Ge may diffuse into the silicon cap. If necessary, a second thin, e.g., 10 nm to 20 nm, tensile-strained pure silicon cap 52 can then be epitaxially grown on top of silicon cap 46, as shown in FIG. 7, which includes a relaxed SiGe film re-crystallized layer 48 and a high defect layer 50.

[0031] In an alternative embodiment of the method of the invention, the process begins with formation of a thick, relaxed SiGe virtual substrate, e.g., several microns thick, as described in related Application 1. Because these substrates contain a high level of threading dislocations reaching the surface, typically ˜1·10⁵cm⁻², it may be possible to reduce these defect levels by the method of the instant invention. Specifically, a thin silicon cap may be used as a less easily damaged seed layer for SPE, implant Si⁻ or Ge⁺ ions while keeping the wafer at an optimum temperature above T_c, to produce a buried amorphous SiGe region, and recrystallize the SiGe by an appropriate anneal. A thin, tensile-strained pure silicon cap 28 may be epitaxially grown on top of layer 24. The Si/Si_1−xGe_xstructure constructed according to the method of the invention is operable to speed switching of pMOS and nMOS transistors.

[0032] Thus, a method for implantation at elevated temperatures for amorphization re-crystallization of Si_1−xGe_xfilms on silicon substrates has been disclosed. It will be appreciated that further variations and modifications thereof may be made within the scope of the invention as defined in the appended claims.