Coating apparatus – Gas or vapor deposition – Crucible or evaporator structure
Reexamination Certificate
2000-01-21
2003-04-01
Bueker, Richard (Department: 1763)
Coating apparatus
Gas or vapor deposition
Crucible or evaporator structure
C261S127000, C261S140100, C261S152000, C392S396000, C392S397000, C392S399000
Reexamination Certificate
active
06540840
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a vaporizer for MOCVD and a method of vaporizing raw material solutions for MOCVD.
2. Description of the Related Arts
Problematic in the development of DRAMs is a reduction in storage capacitance resulting from the miniaturization. Many measures are needed since the capacitance has to be level with that in the precedent generation from the viewpoint of software errors or the like. As a measure for this, increase in the capacitor area has been aimed at by introducing a three-dimensional structure referred to as a stack structure or a trench structure for cell structures exceeding 4M in addition to the planer structure for 1M or less. A dielectric film has also been employed which consists of a thermal oxide film and a CVD nitride film laminated on the poly-Si from the thermal oxide film of the substrate Si (this laminated film is referred to commonly as an ON film). For 16M DRAM, in order to further increase the area contributing to the capacitance, there have been introduced stack types such as a use of the side or a fin type utilizing the back of the plate as well.
Such three-dimensional structures have disadvantageously given rise to an increase in the stages due to the complicated process and a reduction in the yield due to the increased steps, rendering the realization in 256 Mbits or larger DRAMs difficult. For this reason, conceived as one way to further increase the integration degree without altering the current DRAM structures was a switching of the capacitance dielectrics to ferroelectrics having a higher dielectric constant. First attention was paid to a dielectric thin film having a high dielectric constant to a thin film of high-dielectric-constant single-metal paraelectric oxides such as Ta
2
O
5
, Y
2
O
3
and HfO
2
. The relative dielectric constants of Ta
2
O
5
, Y
2
O
3
and HfO
2
are of the order of 28, 16, 24, respectively, which are four to seven times that of SiO
2
.
Nevertheless, application to 256M or larger DRAMs necessitates a three-dimensional capacitor structure. (Ba
x
Sr
1−x
)TiO
3
, Pb(Zr
y
Ti
1−y
)O
3
and (Pb
a
L
1−a
) (Zr
b
Ti
1−b
)O
3
are promising as materials having a higher relative dielectric constant than the above oxides and expected to be applicable to DRAMs. Similarly promising is a Bi-based laminar ferroelectric material having a crystal structure extremely resembling the superconductor. From the viewpoint of low-tension drive and good fatigue characteristics, remarkable attention is being paid recently to SrBi
2
TaO
9
referred to as Y
1
material in particular.
The formation of SrBi
2
TaO
9
ferroelectric thin film is typically carried out by means of practical and promising MOCVD (metal organic chemical vapor deposition).
Raw materials of the ferroelectric thin film are typically three different organometallic complexes, Sr(DPM)
2
, Bi(C
6
H
5
)
3
and Ta(OC
2
H
5
)
5
, which are each dissolved in THF (tetrahydrofuran) solvent for use as a solution. DPM is an abbreviation of dipivaloylmethane.
Table 1 shows the respective material characteristics.
TABLE 1
BOILING POINT (° C.)/
PRESSURE (mmHg)
MELTING POINT (° C.)
Sr(DPM)
2
242/14
78
Bi(C
6
H
5
)
3
270~280/1
201
Ta(OC
2
H
5
)
5
146/0.15
22
THF
67
−109
The system for use in MOCVD comprises a reacting section for subjecting SrBi
2
TaO
9
thin film raw material to a gas phase reaction and a surface reaction for film deposition, a feeding section for feeding SrBi
2
TaO
9
thin film raw material and an oxidizing agent to the reacting section, and a collecting section for collecting reaction products obtained in the reacting section.
The feeding section is provided with a vaporizer for vaporizing the thin film raw material.
Known techniques related to the vaporizer are illustrated in FIG.
12
.
FIG. 12A
shows a so-called metal filter method in which a raw material solution heated to a predetermined temperature is drip fed to a metal filter used with the aim of increasing the area of contact between the ambient gas and the SrBi
2
TaO
9
ferroelectric thin film raw material solution.
This technique however has a deficiency that the metal filter may become clogged after several vaporizations, making the long-term use difficult.
FIG. 12B
depicts a technique in which 30 kgf/cm
2
of pressure is applied to a raw material solution so as to allow the raw material solution to be emitted through 10 &mgr;m pores and expanded for evaporation.
This technique however entails a problem that the pores may ecome clogged as a result of several-times operations, rendering it difficult to endure the long-term use.
In the event that the raw material solution is a mixture solution of a plurality of organometallic complexes, e.g., Sr(DPM)
2
/THF, Bi(C
6
H
5
)
3
/THF and Ta(OC
2
H
5
)
5
/THF and that this mixture solution is vaporized by heating, the solvent (THF in this case) having a highest vapor pressure will be vaporized earlier, with the result that the organometallic complexes may be deposited and adhered onto the heated surfaces, blocking a stable feed of raw materials to the reacting section.
Furthermore, it is demanded in order to obtain a film having a good uniformity by MOCVD that there should be presented a vaporized gas within which the raw material solutions have uniformly been dispersed. However, the above prior art has not necessarily met such a demand.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a vaporizer for MOCVD capable of long-term use without causing any clogging or other inconveniences and ensuring a stable feed of raw materials to the reacting section.
Another object of the present invention is to provide a vaporizer for MOCVD and a method of vaporizing raw material solutions for MOCVD, capable of obtaining a vaporized gas containing uniformly dispersed raw material solutions.
According to a first aspect of the present invention there is provided a vaporizer for MOCVD having a dispersing section and a vaporizing section, wherein the dispersing section comprises a gas passage formed in the interior, a gas introduction port for introducing a carrier gas under pressure into the gas passage, means for feeding a raw material solution to the gas passage, a gas outlet for delivering the carrier gas containing the raw material solution to the vaporizing section, and means for cooling the gas passage, and wherein the evaporizing section comprises a vaporizing tube having one end connected to a reaction tube of an MOCVD system and having the other end connected to the gas outlet of the dispersing section, and heating means for heating the vaporizing tube, the vaporizing section serving to heat and vaporize the raw material solution containing carrier gas delivered from the dispersing section.
According to a second aspect of the present invention there is provided a vaporizer for MOCVD having a dispersing section and a vaporizing section, wherein the dispersing section comprises a gas passage formed in the interior, a gas introduction part for introducing a carrier gas under pressure into the gas passage, means for feeding a raw material solution to the gas passage, and a gas outlet for delivering the carrier gas containing the raw material solution to the vaporizing section, and wherein the vaporizing section comprises a vaporizing tube having one end connected to a reaction tube of an MOCVD system and having the other end connected to the gas outlet of the dispersing section, and heating means for heating the vaporizing tube, the vaporizing section serving to heat and vaporize the raw material solution containing carrier gas delivered from the dispersing section, and wherein the dispersing section includes a dispersing section body having a cylindrical hollow portion, and a rod having an outer diameter smaller than the inner diameter of the cylindrical hollow portion, the rod having at least one spiral groove formed in the external periphery t
Doi Mikio
Fukagawa Mitsuru
Kanno Yoichi
Kusuhara Masaki
Meguro Toshikatu
Bueker Richard
Kabushiki Kaisha Watanabe Shoko
Knuth Randall J.
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