Semiconductor device manufacturing: process – Coating of substrate containing semiconductor region or of... – Insulative material deposited upon semiconductive substrate
Reexamination Certificate
2003-03-27
2004-08-31
Karlsen, Ernest (Department: 2829)
Semiconductor device manufacturing: process
Coating of substrate containing semiconductor region or of...
Insulative material deposited upon semiconductive substrate
C438S789000
Reexamination Certificate
active
06784123
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to a semiconductor technique and more particularly to a silicone polymer insulation film on a semiconductor substrate and a method for forming the film by using a plasma CVD (chemical vapor deposition) apparatus.
2. Description of the Related Art
Because of the recent rise in requirements for the large-scale integration of semiconductor devices, a multi-layered wiring technique attracts a great deal of attention. In these multi-layered structures, however, capacitance among individual wires hinders high speed operations. In order to reduce the capacitance it is necessary to reduce dielectric constant of the insulation film. Thus, various materials having a relatively low dielectric constant have been developed for insulation films.
Conventional silicon oxide films SiO
x
are produced by a method in which oxygen O
2
or nitrogen oxide N
2
O is added as an oxidizing agent to a silicon source gas such as SiH
4
or Si(OC
2
H
5
)
4
and then processed by heat or plasma energy. Its dielectric constant is about 4.0.
Alternatively, a fluorinated amorphous carbon film has been produced from C
x
F
y
H
z
as a source gas by a plasma CVD method. Its dielectric constant ∈ is as low as 2.0-2.4.
Another method to reduce the dielectric constant of insulation film has been made by using the good stability of Si—O bond. A silicon-containing organic film is produced from a source gas under low pressure (1 Torr) by the plasma CVD method. The source gas is made from P-TMOS (phenyl trimethoxysilane, formula 1), which is a compound of benzene and silicon, vaporized by a babbling method. The dielectric constant ∈ of this film is as low as 3.1.
A further method uses a porous structure made in the film. An insulation film is produced from an inorganic SOG material by a spin-coat method. The dielectric constant ∈ of the film is as low as 2.3.
However, the above noted approaches have various disadvantages as described below.
First, the fluorinated amorphous carbon film has lower thermal stability (370° C.), poor adhesion with silicon-containing materials and also lower mechanical strength. The lower thermal stability leads to damage under high temperatures such as over 400° C. Poor adhesion may cause the film to peel off easily. Further, the lower mechanical strength can jeopardize wiring materials.
Oligomers that are polymerized using P-TMOS molecules do not form a linear structure in the vapor phase, such as a siloxane structure, because the P-TMOS molecule has three O—CH
3
bonds. The oligomers having no linear structure cannot form a porous structure on a Si substrate, i.e., the density of the deposited film cannot be reduced. As a result, the dielectric constant of the film cannot be reduced to a desired degree.
In this regard, the babbling method means a method wherein vapor of a liquid material, which is obtained by having a carrier gas such as argon gas pass through the material, is introduced into a reaction chamber with the carrier gas. This method generally requires a large amount of a carrier gas in order to cause the source gas to flow. As a result, the source gas cannot stay in the reaction chamber for a sufficient length of time to cause polymerization in a vapor phase.
Further, the SOG insulation film of the spin-coat method has a problem in that the material cannot be applied onto the silicon substrate evenly and another problem in which a cure system after the coating process is costly.
It is, therefore, a principal object of this invention to provide a method for forming an improved insulation film.
It is another object of this invention to provide an insulation film that has a low dielectric constant and excellent film quality.
It is a still further object of this invention to provide a method for easily forming an insulation film that has a low dielectric constant without requiring an expensive device.
SUMMARY OF THE INVENTION
One aspect of this invention involves a method for forming an insulation film on a semiconductor substrate by using a plasma CVD apparatus including a reaction chamber, which method comprises a step of directly vaporizing a silicon-containing hydrocarbon compound expressed by the general formula Si
&agr;
O
&bgr;
C
x
H
y
(&agr;, &bgr;, x, and y are integers) and then introducing it to the reaction chamber of the plasma CVD apparatus, a step of introducing an additive gas as necessary into the reaction chamber and also a step of forming an insulation film on a semiconductor substrate by plasma polymerization reaction.
In particular, the present invention includes, but are not limited to, the following embodiments:
A method comprises the steps of: (a) vaporizing a silicon-containing hydrocarbon compound to provide a source gas; (b) introducing the source gas into a reaction space for plasma CVD processing wherein a semiconductor substrate is placed; (c) optionally introducing an additive gas selected from the group consisting of an inert gas, an oxidizing gas, and a plasma stabilizing gas, said source gas and said additive gas constituting a reaction gas; and (d) forming an insulation film on the semiconductor substrate by activating plasma polymerization reaction at a temperature of about −50° C. to about 100° C. in the reaction space, wherein the plasma polymerization reaction is activated while controlling the flow of the reaction gas to lengthen a residence time, Rt, of the reaction gas in the reaction space, wherein 100 msec≦Rt,
Rt[s]=
9.42×10
7
(
Pr·Ts/Ps·Tr
)
r
w
2
d/F
wherein:
Pr: reaction space pressure (Pa)
Ps: standard atmospheric pressure (Pa)
Tr: average temperature of the reaction (K)
Ts: standard temperature (K)
r
w
: radius of the silicon substrate (m)
d: space between the silicon substrate and the upper electrode (m)
F: total flow volume of the reaction gas (sccm).
According to the present invention, a silicone polymer film having a micropore structure with a low dielectric constant can be produced. In an embodiment, the dielectric constant of the insulation film can be about 2.50 or lower. In the present invention, the reaction temperature is low, and the residence time is lengthened. Thus, the reaction on the surface of the substrate does not progress quickly, and polymers or oligomers formed in a gaseous phase in the reaction space can accumulate on the surface of the substrate without further reactions, so that the polymer or oligomer structures can remain when accumulating on the surface. As a result, polymers or oligomers (hereinafter simply “polymers”) having structures close to ideal siloxan polymers can accumulate, thereby forming on the substrate a film having a low dielectric constant which is about 2.50 or lower.
In order to remove moisture and improve mechanical strength, the method may further comprise annealing the insulation film. In an embodiment, the annealing may be conducted approximately at 300° C.-450° C. by radiating the insulation film with UV light or electron beams or by using a heater under reduced pressure, thereby forming a film having excellent film quality.
For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention have been described above. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught herein without necessarily achieving other objects or advantages as may be taught or suggested herein.
Further aspects, features and advantages of this invention will become apparent from the detailed description of the preferred embodiments which follow.
REFERENCES:
patent: 5804259 (1998-09-01), Robles
patent: 6107184 (2000-08-01), Mandal et al.
patent: 6352945 (2002-03-01), Matsuki et al.
patent: 6383955 (2002
Hyodo Yasuyoshi
Matsuki Nobuo
Morisada Yoshinori
Umemoto Seijiro
ASM Japan K.K.
Karlsen Ernest
Kilday Lisa
Knobbe Martens Olson & Bear LLP
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