Semiconductor device manufacturing: process – Coating of substrate containing semiconductor region or of... – Insulative material deposited upon semiconductive substrate
Reexamination Certificate
1999-05-21
2002-06-04
Nguyen, Tuan H. (Department: 2813)
Semiconductor device manufacturing: process
Coating of substrate containing semiconductor region or of...
Insulative material deposited upon semiconductive substrate
C438S003000, C438S650000, C438S643000
Reexamination Certificate
active
06399521
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention is generally related to the fabrication of integrated circuits (ICs) and, more specifically, to the fabrication of a highly stable conductive electrode barrier using an iridium (Ir) composite film with an adjacent barrier including an oxidized transition, or refractory metal.
Platinum (Pt) and other noble metals are used in IC ferroelectric capacitors. The use of noble metals is motivated by their inherent chemical resistance. This property is especially desirable under high temperature oxygen annealing conditions, such as those seen in the fabrication of ferroelectric capacitors. In addition, chemical interaction between noble metals and ferroelectric materials such as perovskite metal oxides, is negligible.
The above-mentioned noble metals are used as conductive electrode pairs separated by a ferroelectric material. One, or both of the electrodes are often connected to transistor electrodes, or to electrically conductive traces in the IC. As is well known, these ferroelectric devices can be polarized in accordance with the voltage applied to the electrode, with the relationship between charge and voltage expressed in a hysteresis loop. When used in memory devices, the polarized ferroelectric device can be used to represent a “1” or a “0”. These memory devices are ferro-RAM (FeRAM) and metal ferroelectric metal insulator silicon (MFMIS) transistors. Ferroelectric devices are nonvolatile. That is, the device remains polarized even after power is removed from the IC in which the ferroelectric is imbedded.
There are problems in the use of metal, even noble metal electrodes. Pt, perhaps the widely used noble metal, permits the diffusion of oxygen, especially during high temperature annealing processes. The diffusion of oxygen through Pt results in the oxidation of the neighboring barrier and substrate material. Typically, the neighboring substrate material is silicon or silicon dioxide. Oxidation can result in poor adhesion between the Pt and neighboring layer. Oxidation can also interfere with the conductivity between neighboring substrate layers. Silicon substrates are especially susceptible to problems occurring as a result of oxygen diffusion. The end result may be a ferroelectric device with degraded memory properties. Alternately, the temperature of the IC annealing process must be limited to prevent the degradation of the ferroelectric device.
Various strategies have been attempted to improve the interdiffusion, adhesion, and conductivity problems associated with the use of noble metals as a conductive film in IC fabrication. Titanium (Ti), titanium oxide (TiO
2
), and titanium nitride (TiN) layers have been interposed between a noble metal and silicon (Si) substrates to suppress the interdiffusion of noble metal into Si, and to enhance adhesion between layers. However, Ti layers are generally only effective below annealing temperatures of 600 degrees C. After a 600 degree C. annealing, Pt diffuses through the Ti layer to react with silicon, forming a silicide product. Further, the Pt cannot stop the oxygen diffusion. After a high temperature annealing, a thin layer of silicon oxide may be formed on the silicon surface, which insulates contact between silicon and the electrode.
Other problems associated with the annealing of a Pt metal film are peeling and hillock formation. Both these problems are related to the differences in thermal expansion and stress of Pt with neighboring IC layers during high temperature annealing. A layer of Ti overlying the Pt film is known to reduce stress of the Pt film, suppressing hillock formation.
Ir has also been used in attempts to solve the oxygen interdiffusion problem. Ir is chemically stable, having a high melting temperature. Compared to Pt, Ir is more resistant to oxygen diffusion. Further, even when oxidized, iridium oxide remains conductive. When layered next to Ti, the Ir/Ti barrier is very impervious to oxygen interdiffusion. However, Ir reacts with Ti. Like Pt, Ir is also very reactive with silicon or silicon dioxide. Therefore, a bilayered Ir/Ti or Ir/TiN barrier is not an ideal barrier metal.
Co-pending application Ser. No. 09/263,595, entitled “Iridium Conductive Electrode/Barrier Structure and Method for Same”, invented by Zhang et al., and filed on Mar. 5, 1999, discloses a multilayered Ir/Ta film that is resistant to interdiffusion.
Co-pending application Ser. No. 09/263,970, entitled “Iridium Composite Barrier Structure and Method for Same”, invented by Zhang et al., and filed on Mar. 5, 1999, discloses a Ir composite film that is resistant to interdiffusion.
Co-pending application Ser. No. 09/316,661, entitled “Composite Iridium-Metal-Oxygen Barrier Structure with Refractory Metal Companion Barrier and Method for Same,” invented by Zhang et al., and filed on May 21, 1999, now U.S. Pat. No. 6,190,963, discloses an Ir composite film that is resistant to interdiffusion.
It would be advantageous if alternate methods were developed for the use of Ir as a conductor, conductive barrier, or electrode in IC fabrication. It would be advantageous if the Ir could be used without interaction to an underlying Si substrate.
It would be advantageous if an Ir film could be altered with other conductive metals to improve interdiffusion properties. Further, it would be advantageous if this improved type of Ir film could be layered with an interposing film to prevent the interaction of Ir with a silicon substrate.
It would be advantageous if the barrier interposed between the Ir composite film and the silicon substrate could be used as the gate dielectric of a transistor.
It would be advantageous if the above-mentioned Ir-metal film could resist the interdiffusion of oxygen at high annealing temperatures. It would also be advantageous if the Ir-metal film was not susceptible to peeling problems and hillock formation.
It would be advantageous if the Ir-metal film could be produced which remains electrically conductive after annealing at high temperatures and oxygen ambient conditions.
SUMMARY OF THE INVENTION
Accordingly, a highly temperature stable conductive barrier layer for use in an integrated circuit is provided. The barrier comprises an underlying silicon substrate, a first barrier film including an oxidized refractory metal barrier overlying the substrate, and an iridium-refractory metal-oxygen (Ir—M—O) composite film overlying the first barrier film. The refractory metal is used to help stuff the grain boundaries of Ir polycrystals, improving structural stability.
Typically, the first barrier film is selected from the group of materials consisting of TiO
2
, Ta
2
O
5
, Nb
2
O
5
, ZrO
2
, Al
2
O
3
, and HfO
2
. The first barrier layer has a thickness in the range of approximately 2 to 100 nanometers (nm). The first barrier is used as a barrier to separate the silicon substrate from the bottom electrode Ir composite film. It also acts as a gate dielectric in a metal ferroelectric metal insulator silicon (MFMIS) memory.
The Ir—M—O composite film remains conductive after high temperature annealing processes in an oxygen environment. Further, the Ir—M composite film resists hillock formation, and resists peeling. Specifically, the Ir composite film includes the following materials: Ir—Ta—O, Ir—Ti—O, Ir—Nb—O, Ir—Al—O, Ir—Zr—O, and Ir—Hf—O. Typically, the Ir—M—O composite film has a thickness in the range of approximately 10 to 500 nm.
In some aspects of the invention, the barrier is used to form an electrode in a ferroelectric device. Then, a ferroelectric film overlies the Ir—M—O film. A conductive metal film made of a noble metal, the above-mentioned Ir—M composite film, or multilayered conductive top electrode overlies the ferroelectric film. The ferroelectric film is capable of storing charges between the top and Ir—M—O electrodes.
Also provided is a method for forming a highly temperature stable conductive barrier overlying an integrated circuit substrate. The method comprising the steps of:
a) through PVD, CVD, or MOCVD processes, forming a first barrier layer, as described above,
Hsu Sheng Teng
Zhang Fengyan
Huynh Yennhu B.
Krieger Scott C.
Nguyen Tuan H.
Rabdau Matthew D.
Ripma David C.
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