Etching a substrate: processes – Gas phase etching of substrate – Application of energy to the gaseous etchant or to the...
Reexamination Certificate
1997-12-31
2003-10-21
Sergent, Rabon (Department: 1711)
Etching a substrate: processes
Gas phase etching of substrate
Application of energy to the gaseous etchant or to the...
C134S001100, C134S001200, C216S067000, C252S079100
Reexamination Certificate
active
06635185
ABSTRACT:
FIELD OF INVENTION
The present invention relates generally to dry etching and cleaning. More specifically, this invention relates to the use of a family of fluorinated carbonyl compounds for the plasma etching of semiconductor materials and for the cleaning of apparatus used in the manufacture of semiconductors.
BACKGROUND OF THE INVENTION
Semiconducting devices are manufactured by the repetitive application of four basic operations to a wafer, namely: layering, patterning/etching, doping, and heat treatments. Of particular interest herein is patterning/etching which involves the selective removal of material from the surface of the wafer. More specifically, material is removed by applying a photoresist to a wafer's surface in a particular geometric pattern selectively and then exposing the wafer to a chemical etchant. Those areas of the wafer that are covered by the photoresist are protected from the etchant, while those that are left exposed are removed to some degree by the etchant. Consequently, material is removed in a geometrical pattern as defined by the photoresist. The term “etching” refers to this selective removal of material.
There are basically two types of etching, wet and dry. Wet etching involves the use of liquid corrosive reagents that react with the unprotected material on the wafer's surface and form soluble products which are then carried away by a solvent. Dry etching refers to plasma and plasma-generated methods which employ energetic gas molecules, ions, and/or free radicals that remove material from a wafer's unprotected surface either chemically by reacting with the material, or physically by bombarding the surface. This plasma process can be used also to clean surfaces of reactors and other apparatus used in the manufacture of semiconductors. Thus, discussion directed to etching and etchants herein applies also to cleaning applications. Other terms commonly applied to these plasma processes include plasma etching, reactive-ion etching, high-density plasma etching, ion milling, reactive ion milling, chemical ion beam etching, and sputter etching. Recently, the industry has been moving away from wet etching and toward dry etching due to the more refined patterning control the latter offers.
As the semiconductor industry moves toward dry etching, environmental concerns grow over the use and disposal of the etching chemicals used and the by-products which are formed. In etching, a portion of the etching chemical tends not to react and exits in the effluent from the reaction, along with various reaction by-products. Venting of such etching chemicals is coming under increased scrutiny.
Traditional etching chemicals, such as, for example, carbon tetrafluoride, hexafluoroethane, perfluoropropane, nitrogen trifluoride, bis(trifluoromethyl) disulfide, and sulfur hexafluoride, and their perfluorinated by-products, such as carbon tetrafluoride and hexafluoroethane, have relatively high Global Warming Potentials. Global Warming Potential (herein “GWP”) refers to a compound's ability, relative to CO
2
, to contribute to global warming. GWP is a calculated value based on a compound's estimated atmospheric lifetime and its ability to absorb infrared radiation. GWPs are reported by the Intergovernmental Panel on Climate Change (IPCC) for different time horizons, with a 100-year horizon being the most common. As used herein, a GWP is based on a 100-year horizon unless otherwise stated. Increasingly, governments and international treaties are requiring that the venting of such high-GWP chemicals be reduced or eliminated. As a consequence of these restrictions, the commercial-availability of these chemicals for semiconductor fabrication is suffering.
Currently, attempts to alleviate the environmental concerns associated with plasma etching and cleaning fall into one of four categories: (1) optimizing etching and/or cleaning processes such that lower amounts of GWP chemicals are emitted into the atmosphere; (2) recycling etching and/or cleaning chemicals from an exhaust stream so that they can be disposed of properly or reused without atmospheric emissions; (3) abating etching and/or cleaning chemicals in exhaust streams by chemical reaction or burn boxes which incinerate and render the unreacted etching and/or cleaning chemical effluents inoffensive, particularly with regard to GWP; and (4) selecting or developing various replacement chemicals for etching and/or cleaning duty. Regarding the first approach, advancements in optimizing the etching and cleaning processes to reduce releases are being made continuously; however, the advancements are not capable of reducing emissions to acceptable levels. Regarding the recycling and abating approaches, although emissions can be reduced, the cost of implementation is relatively high, and, again, the reduction levels still tend to be inadequate. Therefore, replacing the traditional etching chemicals with environmentally-acceptable substitutes appears to be a solution that should be considered.
Accordingly, a need exists for etching and cleaning compositions which have acceptable performance, but which do not contribute significantly to global warming when by-products or unreacted chemicals are vented to the atmosphere. The present invention fulfills this need among others.
DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
The present invention identifies a family of fluorinated carbonyl compounds which are useful as etchant compounds and which are environmentally acceptable. More specifically, the family of fluorinated carbonyl compounds includes compounds having one of the following two formulas:
F—CO—[(CR
1
R
2
)
m
—CO]
n
—F (1)
wherein:
m=0, 1, 2, 3, 4, or 5
n=0 or 1
R
1
& R
2
represent H, F or C
x
H
y
F
z
; wherein:
x=1 or 2; and
y+z=2x+1;
F—CO—R
3
—CO—F (2)
wherein:
R
3
represents CR
4
═CR
5
, R
6
R
7
C═C or C≡C; wherein:
R
4-7
represent H, F, or C
x
H
y
F
z
; wherein:
x=1 or 2; and
y+z=2x+1.
These compounds, herein referred to as “etchant compounds,” regardless of their use as etchants or cleaners, tend to have low GWPs and to form by-products having low-GWP during plasma etching/cleaning such that the reaction effluent of unreacted compounds and reaction by-products is relatively benign to the environment. In addition to being environmentally acceptable, these etchant compounds react surprisingly well with a variety of materials under plasma etching conditions. Examples of such materials include, but are not limited to: dielectrics such as carbides, borides and silicides of metals or semi-metals, for example, tungsten silicide; insulators, such as oxides, nitrides of metals or semi-metals, for example, silicon dioxide, silicon nitride, silicon oxynitride, boronphosphorus silicate glass, and fluorosilicate glass; III-V semiconductor compounds such as indium phosphide; elemental materials, such as silicon, polycrystalline silicon, tungsten, titanium, vanadium, germanium, silicon-germanium; and combination of two or more thereof.
One aspect of the invention is the provision of a method for etching using the above-identified etchant compounds. In one embodiment, the method comprises subjecting a material under plasma etching conditions to an etching composition which has a GWP of no greater than about 3000 and which comprises an etchant compound of Formula (1) wherein n=1 or an etchant compound of Formula (2). In another embodiment, the method comprises subjecting a material under plasma etching conditions to an etching composition comprising an etchant compound of Formula (1) wherein m&n≧0 or an etchant compound of Formula (2). In yet another embodiment, the method comprises subjecting a non-silicon or non-silicon dioxide material under plasma etching conditions to an etching composition comprising an etchant compound of Formula (1) or (2).
Another aspect of the invention is the provision of a method for cleaning accumulated films or residue from a surface of an apparatus,
Demmin Timothy R.
Fathimulla Mohammed A.
Luly Matthew H.
Allied-Signal Inc.
Chess Deborah M.
Sergent Rabon
Szuch Collen D.
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