Topcoat process to prevent image collapse

Details Topcoat process to prevent image collapse Topcoat process to prevent image collapse

2000-12-22

2003-12-02

Huff, Mark F. (Department: 1756)

Radiation imagery chemistry: process, composition, or product th

Imaging affecting physical property of radiation sensitive...

Forming nonplanar surface

C430S311000, C430S315000, C430S329000, C430S330000, C430S331000

Reexamination Certificate

active

06656666

ABSTRACT:

FIELD OF THE INVENTION
The invention relates generally to photolithographic techniques, and particularly, but not by way of limitation, to a method for preventing the collapse of the image pattern during the stage of drying the image.
BACKGROUND
Photolithographic processes are well-known in the art for use in the manufacture of semiconductor devices. Lithography generally involves transferring a desired pattern, such as a circuit pattern, through a resist layer onto an underlying silicon substrate. The first step of the process generally involves forming a resist layer on the substrate layer. The resist layer is then exposed to patterned radiation to cause dissolution differentiation in the resist layer. The resist layer is then developed generally with liquid developer. The pattern is then transferred to the underlying silicon substrate with transfer techniques such as etching or ion implantation.
There is an increasing desire in the industry for higher circuit density in microelectronic devices which are made using lithographic techniques. One method of increasing the number of components per chip is to decrease the minimum feature size of the chip, which requires higher lithographic resolution. There is a goal in the industry to reduce the feature size below 0.20 microns.
Following exposure to light (or electrons) the resist is developed typically using a wet chemical process. The developing chemicals and selective portions of the resist are rinsed away and the resist is dried. A problem arises in that the resist pattern may tend to collapse under the surface tension forces of the rinsing liquid especially as the liquid is withdrawn during the drying process. This tendency to collapse is exacerbated by high aspect ratio resist patterns required as the minimum feature size of the chip devises decreases.
Chemically amplified resists are based on an aqueous solution of tetraethyl ammonium hydroxide with a water based rinse, as shown in, for example, U.S. Pat. No. 5,580,694 to Allen and Semiconductor Lithography, chapters 2 and 10, by W. Moreau, Plenum Press, 1987.
“Mechanism of Resist Pattern Collapse During Development Process”, A. Tanaka et al.,
J. Appl. Physics
, Vol. 32, pp. 6059-6064, 1993, and “Pattern Collapse in the Top Surface Imaging Process after Dry Development,” M. Mori et al.,
J. Vac. Sic. and Tech
., Vol. B16, pp. 3477-47, 1999, describe the image collapse of resist images with aspect ratio (thickness to line width) caused by the high surface tension of water (80 dynes/cm
2
) rinse drying step exerting a physical force on the walls of the resist image.
A method of developing a resist using hot water to reduce the surface tension of water is shown in U.S. Pat. No. 5,474,877 to Suzuki, but, according to Tanaka, an order of magnitude in surface tension for the rinse/dry step is needed to address submicron image collapse. Supercritical fluids such as carbon dioxide have very low surface tension (<1), as shown in U.S. Pat. No. 5,665,527 to Allen and “Imaging Polymers with Supercritical Carbon Dioxide,” C. Ober et al.,
Advance Materials
, Vol. 9, pp. 1039-1043, 1997, and have been used to develop fluoropolymers as negative images. Water-based conventional chemically amplified resists remain the workhorse formulations for 248 nm, 193 nm and 157 nm generations. Water itself is sparingly soluble in supercritical CO
2
, as shown in J. Hyatt's “Liquid and Supercritical Carbon Dioxide as Organic Solvents,”
J. Org. Chem
., Vol. 49, pp. 5097-5101, 1984. To remove water, an alcohol rinse has been suggested in Tanaka, but most of the amplified resist are susceptible to attack or dissolution in polar solvents. If a water rinse is used in a manufacturing line, the subsequent transport of the “wet resist” without drying to the next process station is necessary to prevent image collapse. Some polymers such as polyethers, e.g., polyethylene and polypropylene glycol, as shown in “Solubility of Homopolymers and Copolymers in Carbon Dioxide,” M. O'Neill et al.,
Ind. Eng. Chem. Res.
, Vol. 37, pp. 3067-3079, 1998 and “On the Effect of Polymer Fractionation on the Phase Equilibrium in CO
2
and Polyethylene Glycol Systems,” J. Lopes et al.,
J. Supercritical Fluid
, Vol. 16, pp. 261-267, 2000, as well as fluorinated polyesters FC-430, a registered trademark of 3M Corporation, are soluble in water, xylene, and fluid carbon dioxide.
Accordingly, means are required to stabilize a resist image, particularly an image of high aspect ratio, under conditions that do not distort the image.
SUMMARY OF INVENTION
Means are provided to stabilize a resist image, particularly an image of high aspect ratio, under conditions that do not distort the image. Such means comprise the steps of:
providing a developed resist image;
overcasting said image with a stabilizing layer; and
removing said stabilizing layer.
These means provide for the stabilization, against the withdrawal of water, of the image and its protective topcoat layer with liquid or supercritical CO
2
. Subsequent removal of the CO
2
removes the topcoat and dries the resist image without distorting, removing, or collapsing the image.
According to an embodiment of the invention, the resist is cast from and developed in aqueous solutions.
According to an embodiment of the invention, the resist is cast from and developed in organic solutions.
According to an embodiment of the invention, the resist is a negative resist.
According to an embodiment of the invention, the resist is a positive resist.
According to another embodiment of the invention there is provided the substantially non-distorted resist image formed by the inventive process.
According to yet a further embodiment of the invention, there is provided the semiconductor device and other structures fabricated using the resist image of the inventive process.
Still other objects and advantages of the present invention will become readily apparent by those skilled in the art from the following detailed description, wherein it is shown and described preferred embodiments of the invention, simply by way of illustration of the best mode contemplated of carrying out the invention. As will be realized the invention is capable of other and different embodiments, and its several details are capable of modifications in various obvious respects, without departing from the invention. Accordingly, the description is to be regarded as illustrative in nature and not as restrictive


REFERENCES:
patent: 5326672 (1994-07-01), Tanaka et al.
patent: 5374503 (1994-12-01), Sachdev et al.
patent: 5474877 (1995-12-01), Suzuki
patent: 5665527 (1997-09-01), Allen et al.
patent: 5977041 (1999-11-01), Honda
patent: 6067728 (2000-05-01), Farmer et al.
patent: 6240936 (2001-06-01), DeSimone et al.
patent: 6319853 (2001-11-01), Ishibashi et al.
patent: 6334266 (2002-01-01), Moritz et al.
patent: 6358673 (2002-03-01), Namatsu
patent: 6398875 (2002-06-01), Cotte et al.
patent: 07-020637 (1995-01-01), None
patent: 09-034116 (1997-02-01), None
Ober, C.K., et al., “Imaging Polymers with Supercritical Carbon Dioxide,”Advanced Materials, vol. 9, No. 13, 1997, pp. 1039-1043.
Mori, S., et al., “Pattern Collapse in the Top Surface Imaging Process after Dry Development,”J. Vac. Sci. Technol. B, vol. 16, No. 6, Nov./Dec. 1998, pp. 3744-3747.
Tanaka, T., et al., “Mechanism of Resist Pattern Collapse During Development Process,”Jpn. J. Appl. Phys.,vol. 32, Pt. 1, No. 12B, 1993, pp. 6059-6064.
John A. Hyatt, “Liquid and Supercritical Carbon Dioxide as Organic Solvents,”J. Org. Chem.,Vo. 49, 1984, pp. 5097-5101.
Lopes, J.A., et al., “On the Effect of Polymer Fractionation on Phase Equilibrium in CO2+poly(ethylene glycol)s Systems,”The Journal of Supercritical Fluids, vol. 16, 2000, pp. 261-267.
Jackson, K., et al., “Water Solubility Measurements in Supercritical Fluids and High-Pressure Liquids Using Near-Infrared Spectroscopy,”Analytical Chemistry, vol. 67, No. 14, Jul. 15, 1995, pp. 2368-2372.
O'Neill, M. L., et al., “Solubility of Homopolymers and Copolymers in Carbon Dioxide,”Ind. Eng. Chem. Res.,No. 37

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