Method for growing thin oxide films

Details Method for growing thin oxide films Method for growing thin oxide films

2000-10-13

2003-10-14

Kunemund, Robert (Department: 1765)

Single-crystal, oriented-crystal, and epitaxy growth processes;

Forming from vapor or gaseous state

With decomposition of a precursor

C117S104000, C117S106000, C117S107000, C117S948000

Reexamination Certificate

active

06632279

ABSTRACT:

REFERENCE TO RELATED APPLICATION
This application claims priority under 35 U.S.C. §119(a) to Finnish patent application number 19992223, filed Oct. 14, 1999.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the fabrication of oxide films by the Atomic Layer Epitaxy (ALE) process, which is generally also known by the name of Atomic Layer Deposition (ALD). The invention relates in particular to a process for the fabrication of thin oxide films by the ALD method by using an oxygen-containing organometallic compound as the oxygen source material.
2. Description of the Related Art
The continual decrease in size of microelectronics components is leading to a situation in which SiO
2
can no longer be used as the gate oxide in metal oxide semiconductor field effect transistors (MOSFET), since, in order to achieve the required capacitances, the SiO
2
layer should be made so thin that the tunneling current would grow detrimentally high in terms of the functioning of the component. To avoid this problem, SiO
2
has to be replaced with an insulator having a higher dielectric constant. In this case, the insulator may be in a thicker layer than SiO
2
.
Materials having sufficiently high dielectric constants are numerous, but there is the problem that the insulator must be prepared on top of silicon so that:
either a very thin or no SiO
2
layer forms between the silicon and the insulator, which reduces the total capacitance according to the equation
1/C(tot)=1/C(insulator)+1/C(SiO
2
),
there are very few electrically active error states on the interface between the silicon and the insulator, because the charge trapped in them has a negative effect on transistor properties such as threshold voltage, transconductance and stability, and
the thickness and uniformity of the insulator are precisely controlled.
Without a thin SiO
2
layer on the interface between the silicon and the insulator it is difficult to produce a situation in which there would be very few electrically active error states on the interface. Thus it would be preferable that the structure of the interface would be an Si—SiO
2
insulator wherein the thickness of the SiO
2
layer would be one or two atom layers.
When an oxide film is deposited on silicon, the surface of the silicon tends to oxidize, forming a SiO
2
layer which is too thick. The oxidation of silicon may be due to reactions with the oxygen source used in the process, reactions with the oxide insulator, or diffusion of oxygen. If the insulator selected is a metal oxide thermodynamically more stable than SiO
2
(e.g. ZrO
2
, HfO
2
, Al
2
O
3
), oxidation can take place only under the effect of the oxygen source used in the deposition process. On the other hand, if the process is carried out at a sufficiently low temperature, the formation of an SiO
2
layer may be hindered kinetically even if it were thermodynamically possible.
ALD (ALE, ALCVD) is a process, described, for example, in U.S. Pat. No. 4,058,430, for the growing of thin films. In the process, a thin film is deposited by means of alternating saturated surface reactions. These reactions are implemented by directing gaseous or vaporized source materials alternately into the reactor and by rinsing the reactor with an inert gas between the source material pulses (T. Suntola, Thin Solid Films 215 (1992) 84; Niinistö et al., Materials Science and Engineering B 41 (1996) 23). Since the film grows through saturated surface reactions, the growth is self-controlled, in which case controlling the film thickness by the number of reaction cycles is precise and simple. Films deposited by the ALD process are of uniform thickness over even large surface areas, and their conformality is excellent. Process technology and equipment are commercially supplied under the trade mark ALCVD™ by ASM Microchemistry Oy, Espoo, Finland.
The metal source materials used in the oxide processes in ALD are metal compounds of many types, in particular halides, alkoxides, &bgr;-diketonates, alkyls, or cyclopentadienyls (for example, M. Leskelä and M. Ritala, Journal de Physique IV 9 (1999) Pr8-837; Niinistö et al., Materials Science and Engineering B 41 (1996) 23). The most commonly used oxygen source materials are water, hydrogen peroxide and ozone. Alcohols, oxygen and nitrous oxide have also been used. Of these, oxygen reacts very poorly at the temperatures below 600° C. commonly used, but the other oxygen sources are highly reactive with most of the metal compounds listed above. On the other hand, these oxygen sources may also oxidize the silicon surface, thus producing the excessively thick intermediate layer of SiO
2
previously described between the silicon and the oxide film.
The total reaction of a typical pair of source materials, a metal oxide and water, can be presented in the following form
M(OR)
a
+a/
2H
2
O→MO
a/2
+a
ROH,
where M stands for a metal, R is a hydrocarbon, and a is the valence of the metal M. Metal alkoxides may also break down thermally, producing the corresponding metal oxides. However, this is not desirable in the ALD process, because the most important characteristic—self-control of the deposition—is lost through thermal breakdown.
Drozd et al. in their article describe an ALD process in which an oxide made up of oxides of aluminum and chromium is produced by exposing a substrate consisting of a silicon crystal to alternate pulses of chromyl chromide (CrO
2
Cl
2
) and trimethyl aluminum (Al(CH
3
)
3
) (Drozd et al., Applied. Surface Science 82/83 (1994) 587). However, relatively few metal oxochlorides are volatile at temperatures below 500° C., a fact which limits the usability of processes of this type in particular in applications of the semiconductor industry, where process temperatures above 500° C. are not desirable.
The object of the present invention is to eliminate the problems associated with the prior art and to provide an entirely novel solution to the problem of growing thin oxide films by ALD.
SUMMARY OF THE INVENTION
One aspect of the invention involves a method for growing thin oxide on the surface of a substrate. The surface of the substrate is alternately reacted with a metal source material and an oxygen source material. Advantageously, the oxygen source material is a boron, silicon, or metal compound which has at least one organic ligand and where an oxygen is bonded to at least one boron, silicon or metal atom.
According to the first preferred embodiment of the method of the invention, oxygen-containing organometallic compounds (M(OR)
a
) are used in the process not only as the oxygen source material but also as a second metal source material. The oxygen-containing organometallic compounds react with the metal compound used as the metal source material. According to the first embodiment of the invention, the same metal is used in the oxygen source material and the metal source material.
According to a second preferred embodiment of the invention, different metals are used, in which case more complicated oxide structures can be grown. According to a third preferred embodiment of the invention, the metal source material also contains oxygen. In this case the source materials are preferably two alkoxides.
According to a fourth preferred embodiment of the invention, a protective layer is deposited on the surface of a readily oxidizing substrate material. The protective layer is typically fewer than 20, preferably fewer than 10, and especially preferably approximately 1-5 atom layers thick. When the substrate has been covered with a film thus deposited, the deposition is continued by some other process, for example, by using water or hydrogen peroxide as the oxygen source material.
According to a fifth preferred embodiment of the invention, the substrate material, typically silicon, is treated in order to remove the native oxide before the growing of the film.


REFERENCES:
patent: 4058430 (1977-11-01), Suntola et al.
patent: 5922405 (1999-07-01), Kim et al.
patent: 6037003 (2000-03-01), Gordon et al.
patent: 6258157 (2001-07-

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