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Electrochemical and Solid-State Letters, 7 5 G108-G111 2004

0013-4651/2004/7 5 /G108/4/$7.00 The Electrochemical Society, Inc.

Low Resistivity p Polycrystalline Silicon Deposition at Low Temperatures with SiH4 BCl3
S. B. Herner,a,*,z M. Konevecki,a U. Raghuram,a S. Sivaram,a and M. H. Clarkb
a b

Matrix Semiconductor, Santa Clara, California 95054, USA University of Florida, Gainesville, Florida 32611, USA

The deposition of p polycrystalline silicon lms on SiO2 substrates by SiH4 /BCl3 gases has been characterized. Films were deposited at temperatures as low as 460C with an as-deposited resistivity of 3560 130 cm with good step coverage in oxide trenches. The extracted activation energy for silicon deposition was 0.6 eV for temperatures between 490 and 580C and boron concentration of 2.0 0.4 1021/cm3 , compared with 0.2 eV for p silicon deposition by SiH4 /B2 H6 for similar conditions. Silicon lms deposited by SiH4 /BCl3 are polycrystalline with low resistivities as-deposited at 460C, whereas lms deposited by SiH4 /B2 H6 are amorphous at deposition temperatures 520C. 2004 The Electrochemical Society. DOI: 10.1149/1.1691531 All rights reserved. Manuscript submitted August 21, 2003; revised manuscript received October 27, 2003. Available electronically March 18, 2004.

Heavily doped silicon lms have many applications for integrated circuits ICs ; as gates, line resistors, and local interconnects in complementary metal oxide semiconductor CMOS transistors, and as sources, channels, and drains in thin lm transistors.1,2 By doping the silicon lm in situ, the need for ion implantation and associated process steps is minimized. Silicon lms can be deposited as amorphous, single crystal, or polycrystalline polysilicon . When in situ doped lms are deposited amorphous, they must be annealed at temperatures in excess of 550C to crystallize the lm, to activate the dopant s , and obtain a low resistivity lm. However, this elevated anneal temperature makes lm formation incompatible for many temperature-sensitive IC applications. Such applications include polysilicon-based thin lm transistors for liquid crystal displays, where the devices are deposited on glass substrate.3 A wider range of glass substrates becomes available with decreased process temperature, and if decreased enough, enables polysilicon deposition on plastic substrates.4 The recent development of polysiliconbased devices that can be stacked on top of one another has increased the desire for low-temperature deposition.5,6 Polysilicon deposition temperature of less than 475C is one enabling factor for the use of low resistivity aluminum interconnects between the polysilicon devices, instead of more thermally stable but higher resistivity materials like TiSi2 or tungsten.7 The ability to deposit doped polysilicon lms at low temperatures with a low resistivity as deposited is therefore desirable. Typically, polysilicon lms are deposited at temperatures in excess of 500C to maintain high deposition rates and therefore high wafer throughput. However, p-type dopant gases have been shown to increase the deposition rates of silicon compared to undoped or n-type dopant gases.8,9 In situ p -doped polysilicon can be deposited with various source gases. The most widely used p-type doping source for silicon is diborane, B2 H6 . 10-13 Diborane and silane gases can deposit silicon lms with boron dopant concentrations greater than 1 1021 B/cm3 , with low, as-deposited resistivities reported at deposition temperatures of 520C.10 However, at deposition temperatures less than 520C, p silicon lms deposited with SiH4 /B2 H6 gases are amorphous as-deposited, and require a second, higher temperature anneal ( 550C) to transform them into low resistivity states. A second drawback of B2 H6 as a p-type source gas is the nonuniformity of the boron distribution across wafers in batch furnaces at deposition temperatures that produce polycrystalline silicon. Low-pressure chemical vapor deposition LPCVD of silicon is typically done in large batch-type furnaces that hold 50 or more wafers to achieve high per wafer throughput and low cost. The boron concentration has been shown to vary from 1 1021/cm3 to

greater than 6 1021/cm3 for a 65 wafer 150 mm diam batch in a horizontal furnace deposited with and SiH4 /B2 H6 gases at a temperature of 550C.12 This nonuniformity is not acceptable for large volume production. The nonuniformity of the dopant distribution can be reduced by using disilane (Si2 H6 ) gas with B2 H6 and reducing the deposition temperature to 350C: boron concentration nonuniformity of 10% was achieved for a 100 wafer 150 mm batch.12 However, at a deposition temperature of 350C, lms deposited with Si2 H6 /B2 H6 were amorphous as-deposited, and required post deposition anneal at 600C to obtain low resistivity. Disilane (Si2 H6 ) is also more expensive than silane. We have characterized the properties of p silicon lms deposited using SiH4 /BCl3 source gases. Of particular interest is the ability to deposit doped crystalline silicon lms on large wafer batches at temperatures as low as 460C with reasonable deposition rates and low resistivity as-deposited. The deposition rate, boron concentration, sheet resistance variance with deposition temperature, and step coverage in trench structures are described, with emphasis on low-temperature properties. Experimental Silicon lms were deposited on 200 mm silicon wafers with 100 nm of thermally grown SiO2 . The deposition tool was a vertical furnace capable of holding 80 wafers with a pitch of 8.6 mm in a quartz boat. The boat was rotated and a full load of wafers was maintained during each deposition. Deposition uniformity was achieved by using ve independently controlled heating element coils outside of the quartz pressure vessel and by using multiple gas injectors. Thickness was measured by ellipsometry on ve points on the wafer. Sheet resistance Rs was measured using a four point probe on 49 points on the as-deposited lms. Boron concentration depth proles were measured by secondary ion mass spectrometry SIMS using a 3 keV O2 ion beam to sputter. The error in concentration for SIMS analysis was estimated to be 20% of the total dose. Step coverage of p polysilicon lms was evaluated on wafers with various trench widths etched into 1 m thick oxide lms. The aspect ratio of the trenches varied from 2.9 to 5.0. To establish how the doping concentration varies with temperature, a single lm of silicon was deposited with temperature and gas ows modulated during deposition to produce doping spikes. The lm was deposited at a pressure of 400 mTorr and an initial temperature of 580C, and the gas ows were 500 sccm SiH4 , 700 sccm He, and 10 sccm of 1.5% BCl3 bal. He . Helium was used to mix the reactive gases and improve lm thickness and sheet resistance Rs uniformity. After deposition of the initial boron-doped spike at 580C, 1.5% BCl3 and He gas ows were discontinued in order to deposit undoped silicon. After depositing approximately 150 nm of undoped silicon, the ow of SiH4 was then discontinued, halting

* Electrochemical Society Active Member.

z

E-mail: brad@matrixsemi.com

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Figure 1. Boron SIMS concentration depth prole for a typical temperature modulation-doped polysilicon lm. The lm was deposited at 400 mTorr and gas ows of 500 sccm SiH4 , 10 sccm 1.5% BCl3 bal. He , and 700 sccm He. The deposition temperature of each spike and the boron concentration (B/cm3 ) is noted in the graph.

Figure 2. Steady-state deposition rates after incubation time of p polysilicon lms with various concentrations of boron. Films were deposited on SiO2 substrates at 400 mTorr, with 500 sccm SiH4 and 700 sccm He. The ow of 1.5% BCl3 bal. He was varied with each deposition.

deposition, and the ow of He restarted to maintain pressure at 400 mTorr. The temperature was then reduced to 550C and the wafers were allowed to equilibrate at the new temperature for 60 min in the He ambient. Silane and boron trichloride gas ows were restarted after temperature equilibration at 550C to produce a second borondoped spike, followed again by undoped silicon deposition. The entire process was repeated at temperatures of 520 and 490C. In this way the concentration of boron was determined with different deposition temperatures for the same gas ows in one lm. The same technique was repeated for different ows of 1.5% BCl3 at deposition temperatures between 460 and 580C to build a library of boron concentrations with 1.5% BCl3 gas ows at different deposition temperatures. Results and Discussion Figure 1 shows the boron SIMS concentration depth prole for a spike lm on an oxide wafer. The concentration of boron in the silicon lms increased as temperature is decreased. We believe that the decreasing boron concentration is due to enhanced desorption of boron or boron species from the surface. A similar effect has been found in in situ phosphorus-doped silicon deposition.14 The steadystate deposition rates of several p polysilicon lms with different doping concentrations at different temperatures are shown in Fig. 2, and are compared with the undoped silicon deposition rate. Similar to B2 H6 , the addition of BCl3 dopant gas increases the deposition rate relative to undoped silicon.10-12 At a ow of 500 sccm SiH4 , a pressure of 400 mTorr, and a deposition temperature of 520C, the deposition rate of undoped silicon is low enough to make undoped silicon deposition economically unfeasible for thick lms. However, deposition rates of 1-2 nm/min at a temperature of 460C for borondoped silicon lms are still practical for manufacturing purposes. The activation energies for silicon deposition are shown in Fig. 2. Activation energies of 0.6-0.9 eV for polysilicon deposition by SiH4 /BCl3 at temperatures between 490 and 580C were extracted, with the value dependent on doping concentration lower energy for higher concentrations . The decreasing activation energy suggests that higher ows of BCl3 facilitates the adsorption of SiH4 onto the wafer surface.10 In comparison, a value of 0.2 eV was extracted for amorphous p silicon lm deposition using SiH4 /B2 H6 , deposited

at 450-525C and 350-410 mTorr pressure.10 Doping velocity, which is dened as the product of the deposition rate and boron incorporation, is plotted for the SiH4 /BCl3 depositions in Fig. 3. The doping velocity remains relatively constant through the temperature regime, suggesting that the rate limiting step for the reaction is gas diffusion in the furnace in the range 460-580C. In contrast, deposition by SiH4 /B2 H6 was shown to be diffusion-limited at temperatures above 500C, and surface reaction rate-limited at temperatures less than 500C, as indicated by a change in doping velocity at that temperature.12 For SiH4 /B2 H6 , improved boron concentration uniformity of silicon lms across a batch of wafers was achieved by

Figure 3. Doping velocity for one mixture of SiH4 /BCl3 . The lm was deposited at 400 mTorr and gas ows of 500 sccm SiH4 , 10 sccm 1.5% BCl3 bal. He , and 700 sccm He.

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Electrochemical and Solid-State Letters, 7 5 G108-G111 2004

Figure 5. As-deposited sheet resistances of 200 nm thick p polysilicon lms deposited at varying deposition temperatures. Sheet resistance was measured by 4 point probe on 49 points on each wafer. Films were deposited on SiO2 substrates at 400 mTorr, with 500 sccm SiH4 , and 700 sccm He. The ow of 1.5% BCl3 bal. He was varied with each deposition.

Figure 4. Weak beam, dark eld TEM micrographs of 200 nm thick p polysilicon lms. Films were deposited on SiO2 substrates at 400 mTorr, with 500 sccm SiH4 , and 700 sccm He. The ow of 1.5% BCl3 bal. He was controlled to produce doping concentrations of a 2 0.4 1020 B/cm3 , and b 2 0.4 1021 B/cm3 .

reducing the deposition temperature to less than 500C. The improved uniformity was attributed to the change to surface reaction limited regime from diffusion limited. At temperatures greater than 500C, the fast reaction of SiH4 B2 H6 caused B2 H6 to be depleted with increasing distance from the injector, resulting in boron concentration nonuniformity across a batch of wafers. Although SiH4 /BCl3 deposition is diffusion-limited for the range 460-580C, the higher activation energy and slower reaction rate prevents BCl3 from being depleted within the diffusion length of the furnace. And, critically, silicon deposited by SiH4 /BCl3 remains polycrystalline with low resistivity for a deposition temperature of 460C, where SiH4 /B2 H6 deposits amorphous silicon for temperatures 520C. Good dopant distribution inside a vertical batch furnace using SiH4 and BCl3 source gases enabled 60 silicon wafers 200 mm per deposition at 460C with a within-wafer wafer-to-wafer thickness nonuniformity of 2.6% 3.1% 1 , and a sheet resistance withinwafer nonuniformity of 2.8% 16.1% 1 as-deposited. The grain size of polysilicon lms deposited by SiH4 /BCl3 is characterized to compare to lms deposited by SiH4 /B2 H6 . Using the line-intercept technique on transmission electron micrographs Fig. 4 of lms deposited from SiH4 /BCl3 , the grain size for the 2 1020/cm3 (2 1021/cm3 ) doped lm is estimated to be 52 nm 53 nm , with

a one sigma variation of 21 nm 25 nm . These grain sizes are similar for polysilicon lms deposited with SiH4 /B2 H6 at 600C with similar boron concentrations.15 The lms deposited for this study have the expected decrease in sheet resistance with increasing boron concentrations Fig. 5 . It has been shown previously that increasing boron concentrations above 2.0 1021/cm3 will not necessarily result in a decreasing resistivity of the as-deposited lms due to amorphous phase formation.16 A similar phenomenon has been found in polysilicon lms deposited at very low pressures 1 mTorr using SiH4 /B2 H6 . 17 Hence, we have limited the boron concentrations in this study to 2 1021/cm3 or less. We extracted resistivities of 3220 to 3560 cm for the lms with the highest boron concentration (2.0 0.4 1021/cm3 ) at deposition temperatures 460-580C. This range of resistivities does not reect a consistent trend with temperature. Table I shows the theoretical resistivities of single crystalline silicon compared with that measured in the p polysilicon lms deposited at 520C in this study for equivalent carrier and doping concentrations, respectively.18 The as-deposited resistivities are far higher than theoretically predicted. This higher resistivity is due to a small fraction of the dopant is being active, and a relatively low charge carrier mobility caused by grain boundaries and other crystal defects that are scattering centers.18 Despite rough lm surfaces, the step coverage on wafers with topography was excellent, with substantially the same thickness lm on trench sidewalls as on the horizontal surface for the 460C depo-

Table I. Resistivities of single crystal silicon compared with p polysilicon lms in this study. Polysilicon lms were deposited at 520C. Resistivity calculated, cm for single crystal Si with carrier concentration 2 7 2 1020/cm3 1020/cm3 1021/cm3 600 170 100 Resistivity measured, cm for p polysilicon with metallurgical concentration 6260 4320 3260

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for a 60 wafer load in a vertical batch furnace with low resistivities as-deposited. The activation energy for deposition using SiH4 /BCl3 was found to be 0.6 and 0.9 eV for boron doping concentrations 2.0 0.4 and 0.2 0.04 1021/cm3 , respectively, in the temperature range 490 to 580C. Step coverage of the p polysilicon lms in oxide trenches remained excellent at low temperature.

Acknowledgments We thank Carole Jahn for SEM images and Andy Walker for fruitful discussions.
The authors assisted in meeting the publication costs of this article.

References
1. E. Ibok and S. Gang, J. Electrochem. Soc., 140, 2927 1993 . 2. A. Mimura, N. Konishi, F. Ono, J.-I. Ohwada, Y. Hosokawa, Y. A. Ono, T. Suzuki, K. Miyata, and H. Kawakami, IEEE Trans. Electron Devices, 36, 351 1989 . 3. C.-L. Fan and M.-C. Chen, J. Electrochem. Soc., 149, H93 2002 . 4. P. G. Carey, P. M. Smith, S. D. Theiss, and P. Wickboldt, J. Vac. Sci. Technol. A, 17, 1946 1999 . 5. M. Crowley, A. Al-Shamma, D. Bosch, M. Farmwald, L. Fasoli, A. Ilkbahar, M. Johnson, B. Kleveland, T. Lee, T.-Y. Liu, Q. Nguyen, R. Scheuerlein, K. So, and T. Thorp, ISSCC Digest of Technical Papers, p. 284 2003 . 6. S. B. Herner, M. Mahajani, M. Konevecki, E. Kuang, S. Radigan, and S. V. Dunton, Appl. Phys. Lett., 82, 4163 2003 . 7. I. Suni, M. Blomberg, and J. Saarilahti, J. Vac. Sci. Technol. A, 3, 2233 1985 . 8. F. C. Eversteyn and B. H. Put, J. Electrochem. Soc., 120, 106 1973 . 9. A. J. Learn and D. W. Foster, J. Appl. Phys., 61, 1898 1987 . 10. C. M. Maritan, L. P. Berndt, N. G. Tarr, J. M. Butterwell, and G. M. Jenkins, J. Electrochem. Soc., 135, 1795 1988 . 11. P. Joubert, M. Sarret, L. Haji, L. Hamedi, and B. Loisel, J. Appl. Phys., 66, 4806 1989 . 12. J.-I. Shiozawa, Y. Kasai, Y.-I. Mikata, and K. Yamabe, J. Electrochem. Soc., 141, 1334 1994 . 13. L. Haji, L. Hamedi, B. Loisel, M. Gauneau, P. Joubert, and M. Sarret, J. Appl. Phys., 66, 4812 1989 . 14. M. L. Yu, D. J. Vitkavage, and B. S. Meyerson, J. Appl. Phys., 59, 4032 1986 . 15. T. Makino and H. Nakamura, Solid-State Electron., 24, 49 1980 . 16. S. B. Herner and M. H. Clark, J. Vac. Sci. Technol. B, 22, 1 2004 . 17. H.-C. Lin, H.-Y. Lin, C.-Y. Chang, T.-G. Jung, P. J. Wang, R.-C. Deng, and J. Lin, J. Appl. Phys., 76, 1572 1994 . 18. S. M. Sze, Physics of Semiconductor Devices, Wiley, New York 1981 .

Figure 6. Step coverage of p polysilicon lm in 3.7:1 aspect ratio trench as shown by cross-sectional SEM micrograph. Film was deposited at 460C, 400 mTorr with doping concentration 2.0 0.4 1021 B/cm3 .

sition temperature with 2.0 0.4 1021/cm3 boron doping Fig. 6 . These partially lled trenches show that the lm has nucleated evenly on the sidewalls through the depth of the trench. Even smaller width trenches with higher aspect ratios were completed lled by the lm deposition. This highly doped lm has been used to ll similar trenches to make vertical interconnects between vertically stacked polysilicon devices.3 The lms deposited with lower concentrations of boron and at higher deposition temperatures had similar step coverage in trenches not shown . Conclusion Highly p -doped polysilicon lms can be deposited at temperatures as low as 460C with good thickness and doping uniformity