Method for growing germanium epitaxial films

Information

  • Patent Grant
  • 9305779
  • Patent Number
    9,305,779
  • Date Filed
    Tuesday, August 11, 2009
    15 years ago
  • Date Issued
    Tuesday, April 5, 2016
    8 years ago
Abstract
A method for growing germanium epitaxial films is disclosed. Initially, a silicon substrate is preconditioned with hydrogen gas. The temperature of the preconditioned silicon substrate is then decreased, and germane gas is flowed over the preconditioned silicon substrate to form an intrinsic germanium seed layer. Next, a mixture of germane and phosphine gases can be flowed over the intrinsic germanium seed layer to produce an n-doped germanium seed layer. Otherwise, a mixture of diborane and germane gases can be flowed over the intrinsic germanium seed layer to produce a p-doped germanium seed layer. At this point, a bulk germanium layer can be grown on top of the doped germanium seed layer.
Description
BACKGROUND OF THE INVENTION

1. Technical Field


The present invention relates to epitaxial films in general, and in particular to a method for growing germanium epitaxial films on silicon substrates.


2. Description of Related Art


There are two conventional methods for growing single-crystal germanium films on silicon substrates using ultra-high vacuum chemical vapor deposition (UHV-CVD). The first method allows a germanium film to be grown directly on top of a silicon layer, and the second method uses a silicon and silicon germanium buffer layer at the interface.


Since the first method is very selective, a germanium film only grows on a silicon layer and not on any exposed dielectric material. The problem with the first method is that the resultant germanium film is very rough and has a substantially high defect density. Compared with the first method, the second method is not selective at all. Thus, although the second method overcomes the roughness problem, the resultant germanium film occurs on an underlying silicon layer as well as an underlying dielectric layer. The growth on the underlying silicon layer is desired but the growth on the underlying dielectric layer is not.


The present disclosure provides an improved method for growing selective germanium epitaxial films.


SUMMARY OF THE INVENTION

In accordance with a preferred embodiment of the present invention, a silicon substrate is initially preconditioned with hydrogen gas. The temperature of the preconditioned silicon substrate is then decreased, and germane gas is flowed over the preconditioned silicon substrate to form an intrinsic germanium seed layer. Next, a mixture of germane and phosphine gases can be flowed over the intrinsic germanium seed layer to produce an n-doped germanium seed layer. Otherwise, a mixture of diborane and germane gases can be flowed over the intrinsic germanium seed layer to produce a p-doped germanium seed layer. At this point, a bulk germanium layer can be grown on top of the doped germanium seed layer.


All features and advantages of the present invention will become apparent in the following detailed written description.





BRIEF DESCRIPTION OF THE DRAWINGS

The invention itself, as well as a preferred mode of use, further objects, and advantages thereof, will best be understood by reference to the following detailed description of an illustrative embodiment when read in conjunction with the accompanying drawings, wherein:



FIG. 1 is a high-level process flow diagram of a method for growing germanium epitaxial films, in accordance with a preferred embodiment of the present invention; and



FIG. 2 depicts a silicon substrate having a germanium epitaxial film, in accordance with a preferred embodiment of the present invention.





DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

The desired smooth and highly selective germanium layer is formed using a UHV-CVD system. The formation can be completed by using the following gases: hydrogen, 100% silane (SiH4), 100% germane (GeH4), 1% diborane (B2H6) and 1% phosphine (PH3).


Referring now to the drawings and in particular to FIG. 1, there is illustrated a high-level process flow diagram of a method for growing germanium epitaxial films, in accordance with a preferred embodiment of the present invention. Starting at block 10, a silicon substrate is preconditioned with hydrogen gas at 750° C. for 60 minutes, as shown in block 11. The pressure of hydrogen is controlled at 3E−4 mBar.


Next, the temperature is ramped down from 750° C. to 350° C. in 200 minutes in vacuum at 2° C. per minute, as depicted in block 12.


Germane gas at 1.5E−3 mBar is flowed over the preconditioned silicon substrate for 120 minutes, as shown in block 13. This step initiates the layer-by-layer growth for approximately the first ten layers of defect-free single-crystal germanium—an intrinsic germanium seed layer.


The temperature is then ramped back up from 350° C. to 600° C. in 125 minutes in vacuum at 2° C. per minute, as depicted in block 14.


A 1:3 mixture of phosphine and germane gases at 6E−4 mBar is flowed over the intrinsic germanium seed layer for 30 minutes, as shown in block 15. This in-situ doped germanium growth step produces approximately 150 Å of an n-doped germanium seed layer with a phosphorus concentration of 1E21 atoms/cm3. Some of the phosphorus diffuses into the underlying intrinsic germanium seed layer (from block 13) and reduces the stress in the underlying intrinsic germanium seed layer. The stress in the germanium is initially created by the lattice mismatch between germanium and silicon from the intrinsic germanium seed layer and silicon substrate, respectively.


At this point, an uniform bulk single-crystal germanium film having an extremely low level of defects can be grown on top of the n-doped germanium seed layer, as depicted in block 16. For example, germane gas at 1.5E−3 mBar can be flowed over the the n-doped germinanium seed layer for 480 minutes to produce approximately 1 μm of an intrinsic germanium layer. If desired, the bulk germanium layer may be in-situ n-doped or p-doped by injecting some phoshine or diborane, respectively, along with the germane gas.


If a p-doped germanium seed layer is desired in block 15, the phosphine gas can be replaced by diborane gas with slightly different conditions. For example, a 1:1 mixture of diborane and germane gases at 6E−4 mBar is flowed over the intrinsic germanium seed layer for 30 minutes in order to produce a p-doped germanium seed layer. This in-situ doped germanium growth step produces approximately 150 Å of a p-doped layer with a boron concentration of 5E21 atoms/cm3.


The steps shown in blocks 13 and 15 provide an intrinsic (first) germanium seed layer and a doped (second) germanium seed layer, respectively, which are key to the growth of a smooth bulk germanium film layer. The mechanism behind the steps shown in blocks 13 and 15 is that some of the phosphorus diffuses into the underlying germanium and reduces the stress in the underlying germanium. The stress is generated by the lattice mismatch between germanium and silicon. The reduction of stresses results in a smooth bulk germanium growth.


The smooth defect-free germanium film can be used to produce germanium photodetectors with lower dark currents than can be produced with a typical process that does not use the doped step in block 15. The disclosed method also decreases the sensitivity of germanium growth to mask size. With a typical germanium growth, the final germanium thickness varies with the size of the mask opening to the silicon substrate. The overall germanium smoothness, decreased sensitivity to pattern size, and lower dark current make the disclosed method preferred for overall process integration.


With reference to FIG. 2, there is depicted a silicon substrate having a germanium epitaxial film, in accordance with a preferred embodiment of the present invention. As shown, an intrinsic germanium seed layer 22 is grown on top of a silicon substrate 21. A bulk germanium film 24, which can be intrinsic or doped, is grown on top of a doped germanium seed layer that rests on top of intrinsic germanium seed layer 22.


One conventional method for improving overall germanium smoothness and for decreasing germanium growth sensitivity to mask size is to use a silicon-germanium buffer layer. The usage of a silicon buffer layer, however, is not selective and results in germanium growth over exposed nitride and oxide regions as well as over exposed silicon regions. Frequently, nitride or oxide layers are used to mask regions where no germanium growth is desired, and a loss of growth selectivity requires additional processing to remove germanium from the tops of exposed nitride or oxide regions. The method of the present invention does not use any silicon containing buffer layer and therefore provides a very selective germanium growth. The simultaneous smooth germanium growth, low sensitivity to pattern size, and high growth selectivity are key benefits from the steps shown in blocks 12 and 13.


As has been described, the present invention provides an improved method for growing germanium epitaxial films. The method of the present invention can be used to grow single-crystal germanium films that are very selective and yet very smooth and defect-free. The improved germanium growth process allows for simpler processing and yields lower dark currents in germanium P-i-N photodiodes.


While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.

Claims
  • 1. A method for growing germanium epitaxial films, said method comprising: flowing germane gas over a silicon substrate at a first temperature to form an intrinsic germanium seed layer on said silicon substrate;increasing said first temperature of said silicon substrate to a second temperature;flowing a mixture of diborane gas and germane gas over said intrinsic germanium seed layer to produce a doped germanium seed layer; andgrowing a bulk germanium film layer on top of said doped germanium layer.
  • 2. The method of claim 1, wherein said first temperature is approximately 350° C.
  • 3. The method of claim 1, wherein said flowing germane gas further includes flowing germane gas at approximately 1.5E−3 mBar.
  • 4. The method of claim 1, wherein said second temperature is approximately 600° C.
  • 5. A method for growing germanium epitaxial films, said method comprising: flowing germane gas over a silicon substrate at a first temperature to form an intrinsic germanium seed layer on said silicon substrate;increasing said first temperature of said silicon substrate to a second temperature;flowing a mixture of dopant gas and germane gas over said intrinsic germanium seed layer to produce a doped germanium seed layer, wherein said dopant gas contains phosphine; andgrowing a bulk germanium film layer on top of said doped germanium layer.
  • 6. The method of claim 1, wherein said mixture of gases is flowed over said intrinsic germanium seed layer at approximately 6E−4 mBar.
  • 7. The method of claim 1, wherein said bulk germanium film layer is intrinsic germanium film.
  • 8. The method of claim 1, wherein said bulk germanium film layer is doped germanium film.
  • 9. The method of claim 1, wherein said flowing a mixture of said gases further includes flowing said mixture of said gases while increasing temperature from said first temperature to said second temperature.
  • 10. A method for growing germanium epitaxial films, said method comprising: flowing germane gas over a silicon substrate at a first temperature to form an intrinsic germanium seed layer on said silicon substrate;increasing said first temperature of said silicon substrate to a second temperature;flowing a mixture of dopant gas and germane gas over said intrinsic germanium seed layer to produce a doped germanium seed layer, wherein said flowing a mixture of said gases further includes flowing a mixture of said gases over said intrinsic germanium seed layer to produce said doped germanium seed layer capable of reducing crystalline defects in said intrinsic germanium seed layer via lattice mismatch reduction; andgrowing a bulk germanium film layer on top of said doped germanium layer.
US Referenced Citations (63)
Number Name Date Kind
4420258 Burns et al. Dec 1983 A
4507157 Oliver Mar 1985 A
4547072 Yoshida et al. Oct 1985 A
4748617 Drewlo May 1988 A
4921354 SooHoo May 1990 A
5165001 Takagi et al. Nov 1992 A
5281805 Sauer Jan 1994 A
5371591 Martin et al. Dec 1994 A
5430755 Perlmutter Jul 1995 A
5625636 Bryan et al. Apr 1997 A
5674778 Lee et al. Oct 1997 A
5703989 Khan et al. Dec 1997 A
5736461 Berti et al. Apr 1998 A
5828476 Bonebright et al. Oct 1998 A
5834800 Jalali-Farahani et al. Nov 1998 A
6117771 Murphy et al. Sep 2000 A
6242324 Kub et al. Jun 2001 B1
6331445 Janz et al. Dec 2001 B1
6387720 Misheloff et al. May 2002 B1
6400996 Hoffberg et al. Jun 2002 B1
6477285 Shanley Nov 2002 B1
6605809 Engels et al. Aug 2003 B1
6677655 Fitzergald Jan 2004 B2
6680495 Fitzergald Jan 2004 B2
6738546 Deliwala May 2004 B2
6785447 Yoshimura et al. Aug 2004 B2
6795622 Forrest et al. Sep 2004 B2
6850252 Hoffberg Feb 2005 B1
6861369 Park Mar 2005 B2
6936839 Taylor Aug 2005 B2
6968110 Patel et al. Nov 2005 B2
7006881 Hoffberg et al. Feb 2006 B1
7010208 Gunn, III et al. Mar 2006 B1
7043106 West et al. May 2006 B2
7072556 Gunn, III et al. Jul 2006 B1
7082247 Gunn, III et al. Jul 2006 B1
7103252 Ide Sep 2006 B2
7139448 Jain et al. Nov 2006 B2
7215845 Chan et al. May 2007 B1
7218809 Zhou et al. May 2007 B2
7218826 Gunn, III et al. May 2007 B1
7259031 Dickson et al. Aug 2007 B1
7272279 Ishikawa et al. Sep 2007 B2
7315679 Hochberg et al. Jan 2008 B2
7329593 Bauer Feb 2008 B2
7333679 Takahashi Feb 2008 B2
7348230 Matsuo et al. Mar 2008 B2
7356221 Chu et al. Apr 2008 B2
20030026546 Deliwala Feb 2003 A1
20030183825 Morse Oct 2003 A1
20040007724 Murthy Jan 2004 A1
20040146431 Scherer et al. Jul 2004 A1
20040190274 Saito et al. Sep 2004 A1
20050094938 Ghiron et al. May 2005 A1
20060105509 Zia et al. May 2006 A1
20060158723 Voigt et al. Jul 2006 A1
20060238866 Von Lerber Oct 2006 A1
20060240667 Matsuda et al. Oct 2006 A1
20070042570 Dip et al. Feb 2007 A1
20070116398 Pan et al. May 2007 A1
20070202254 Ganguli et al. Aug 2007 A1
20080159751 Matsui et al. Jul 2008 A1
20080240180 Matsui et al. Oct 2008 A1
Foreign Referenced Citations (7)
Number Date Country
0 818 693 Jan 1998 EP
1 067 409 Jan 2001 EP
9314514 Jul 1993 WO
0127669 Apr 2001 WO
0216986 Feb 2002 WO
2004088724 Oct 2004 WO
2007149055 Dec 2007 WO
Non-Patent Literature Citations (17)
Entry
WIPO, International Search Report dated Sep. 17, 2010, International App. No. PCT/US10/44185.
Pruessner et al., “InP-Based Optical Waveguide MEMS Switches with Evanescent Coupling Mechanism”, Journal of Microelectromechanical Systems, vol. 14, No. 5, Oct. 2005.
May et al., “Integrated Process for Silicon Nitride Waveguide Fabrication”, IBM Technical Disclosure Bulletin, vol. 33, No. 2, Jul. 1990.
Matsushita et al., “Narrow CoSi2 Line Formation on SiO2 by Focused Ion Beam”, IEEE Xplore 1999.
“Process Integration”, Cobalt Self-aligned Silicide Process, Chapter 13.
Liu et al., “Design of Monolithically Integrated GeSi Electro-absorption Modulators and Photodetectors on an SOI Plaform”, Optics Express 623, vol. 15, No. 2, Jan. 22, 2007.
Fijol et al., “Fabrication of Silicon-on-insulator Adiabatic Tapers for Low Loss Optical Interconnection of Photonic Devices”.
Yap et al., “Integrated Opteoelectronic Circuits with InP-based HBTs”, Proceedings of SPIE, vol. 4290, 2001.
Roth, “Electroabsorption Modulators for CMOS Compatible Optical Interconnects in III-V and Group IV Materials”, Aug. 2007, (part 1 of 3).
Roth, “Electroabsorption Modulators for CMOS Compatible Optical Interconnects in III-V and Group IV Materials”, Aug. 2007, (part 2 of 3).
Roth, “Electroabsorption Modulators for CMOS Compatible Optical Interconnects in III-V and Group IV Materials”, Aug. 2007, (part 3 of 3).
Kimberling et al., “Electronic-photonic Integrated Circuits on the CMOS Platform”.
Chao et al., “Analysis of Temperature Profiles of Thermo-optic Waveguides”, Fiber and Integrated Optics, vol. 33.
Okyay et al., “Silicon Germanium CMOS Optoelectronic Switching Device: Bringing Light to Latch”, IEEE Transactions on Electron Devices, vol. 54, No. 12, Dec. 2007.
McAulay et al., “All-optical Switching and Logic with an Integrated Optic Microring Resonator”, Proc. of SPIE vol. 5814.
Kik et al, “Erbium Doped Optical Waveguide Amplifiers on Silicon”, MRS Bulletin 23(4), 48, Apr. 1998.
Kimmet, J. S., “M.S. Thesis: Integrated Circuit Fabrication Details,” Rutgers University, 1999; 18 pp.
Related Publications (1)
Number Date Country
20110036289 A1 Feb 2011 US