MIIIN based materials and methods and apparatus for...

Semiconductor device manufacturing: process – Coating with electrically or thermally conductive material – To form ohmic contact to semiconductive material

Reexamination Certificate

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C438S604000, C438S775000

Reexamination Certificate

active

06784085

ABSTRACT:

TECHNICAL FIELD
The present invention is generally directed to the production of Group III metal nitride materials for use as free-standing articles as well as substrates for further processes and/or microelectronic and optoelectronic devices. In particular, the present invention is directed to the production of low-defect density, single-crystal materials and highly-oriented polycrystalline materials utilizing enhanced sputtering techniques.
BACKGROUND
A wide variety of techniques exist for depositing thin films onto substrates in order to achieve desirable properties which are either different from, similar to, or superior to the properties of the substrates themselves. Thin films are employed in many kinds of optical, electrical, magnetic, chemical, mechanical and thermal applications. Optical applications include reflective/anti-reflective coatings, interference filters, memory storage in compact disc form, and waveguides. Electrical applications include insulating, conducting and semiconductor devices, as well as piezoelectric drivers. Magnetic applications include memory discs. Chemical applications include barriers to diffusion or alloying (e.g., galling), protection against oxidation or corrosion, and gas or liquid sensors. Mechanical applications include tribological (wear-resistant) coatings, materials having desirable hardness or adhesion properties, and micromechanics. Thermal applications include barrier layers and heat sinks.
Bulk materials can be used as substrates upon which microelectronic and optical devices are fabricated. Wide bandgap semiconductor materials such as gallium nitride, aluminum nitride, indium nitride and their alloys are being studied for their potential application in microelectronics and opto-electronics. These materials are particularly well suited for short wavelength optical applications, such as green, blue and UV light emitting devices (LEDs and LDs), and visible and solar-blind UV detectors. The use of UV or blue GaN-based LEDs makes possible the fabrication of solid state white light sources, with higher efficiencies and lifetimes 10 to 100 times longer than conventional sources. Additionally, GaN has a region of negative differential mobility with a high peak electron velocity and high-saturated velocity, which can be used for fabricating high-speed switching and microwave components. P-type doping of GaN and AlGaN with relatively high hole concentrations is now readily achieved, and ohmic and Schottky contacts have been characterized for n- and p-type materials. Thus, many of the above devices have or potentially have large, technologically important markets. Such markets include display technology, optical storage technology, and space-based communications and detection systems. Other applications include high temperature microelectronics, opto-electronic devices, piezoelectric and acousto-optic modulators, negative-electron affinity devices and radiation/EMP hard devices for military and space uses.
Attempts to grow low-defect density gallium nitride (GaN) thin films heteroepitaxially on substrates such as sapphire and silicon carbide (SiC) have had limited success. GaN materials heteroepitaxially grown on these substrates suffer from large concentrations of threading defects, typically on the order of 10
−8
−10
−10
cm
−2
, due to the large lattice mismatch between the film and substrate. Threading defects increase leakage currents in diode and FET structures and act as a significant source of noise in photodetectors. As a result, the operation of high performance devices, such as high-speed, high-sensitivity UV photodetectors, and high power, high frequency microelectronic devices, is presently limited. Buffer layers of AIN, GaN, and other materials have been used to reduce the lattice mismatch. However, threading defects and low angle grain boundaries remain in the films. Differences between the film and substrate thermal expansion coefficients also result in stresses in the films.
Accordingly, homoepitaxial growth of GaN thin films on bulk GaN substrates is of great interest. The use of GaN substrates would eliminate the problems due to lattice mismatch and thermal expansion mismatch. Unfortunately, the availability of GaN substrates has been limited due to conventional processing capabilities. This problem has hindered the development of devices based on GaN and related nitride semiconductors. Several obstacles exist to the successful manufacturing and commercializing of high device-quality Group III nitride-based materials, whether in bulk, single-crystal, polycrystalline or epitaxial form, for electronics and other applications. These obstacles generally include cost, reproducibility, and purity.
For instance, gallium nitride has a high equilibrium vapor pressure of nitrogen that results in its decomposition at elevated temperatures. The solubility of nitrogen in gallium metal at room temperature and pressure is very low. As a result, conventional crystal growth methods to produce GaN are not practical. This has led to the development of several alternate bulk growth methods, including high-temperature, high-pressure (15 kbar) solution growth, evaporation, and sublimation.
Currently, aluminum nitride and gallium nitride exist only as polycrystalline or powder forms, or in thin films. Polycrystalline bulk aluminum nitride can be manufactured using powder processing techniques. This process has not yielded semiconductor-grade single crystal material. Formidable problems are associated with such techniques, beginning with the production of pure aluminum nitride powders and then the sintering of oxygen-free and defect-free aluminum nitride. Some of these problems include the production of both high-purity and uniform particle-size powders. The highest purity powders can contain up to 1% of oxygen and binders, such as Y
2
O
3
, that are needed to produce aluminum nitride with a high density. Therefore, high density is achievable at the expense of contamination. Sintering of these aluminum nitride powders is also a difficult process. The covalent nature of aluminum nitride prevents densification of pure aluminum nitride at low temperatures. Aluminum nitride decomposes at high temperatures, such as above 1600° C., thereby preventing densification. Hence, costly sintering aids such as high pressures and impurities are required for producing high-density material. Other problems associated with powder processing of aluminum nitride include maintaining the purity and integrity of the powder, controlling the environment at high sintering temperatures, and the production of defect-free parts. Aluminum nitride is very difficult to manufacture using powder processing techniques without introducing contamination that will have adverse effects on the optical and thermal properties of the material. These impurities can be present in the crystalline lattice structure, and can migrate to the grain boundaries during sintering, causing the infrared absorbance to be high.
As disclosed hereinbelow, it has now been discovered that enhanced sputtering techniques, which are physical vapor deposition (PVD) techniques, can be feasibly utilized to produce low-defect density Group III metal nitride materials of bulk thickness and of device-quality crystal. Magnetron sputtering is traditionally associated with thin film deposition. An advantage of sputter synthesis is that high purity compounds can be formed directly from the high purity source materials. Moreover, the synthesis can be achieved under highly controlled conditions. Nitrogen and Group III metals such as aluminum are readily available, from multiple sources, in ultra-high purity grades (e.g., 99.9999%) for the microelectronics industry. Sputter synthesis is currently the process that most effectively eliminates hydrogen from the bulk, since the sputter environment is controllable to ultra-high vacuum conditions. Through sputter synthesis of Group III nitrides, it is possible to obtain materials that have properties near the bulk properties. Since this takes place un

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