Patent Application
20070235841
1. Field of the Invention
The present invention relates to silicon nanowires and methods for synthesizing them, and more particularly to a silicon nanowire array having controllable orientations and a method for synthesizing such an array.
2. Related Art
In the modem integrated circuit (IC) industry, an important theme of development is smaller and faster ICs with less power consumption. However, as the IC industry gradually evolves from a micro-electronics age to a nano-electronics age, conventional semiconductor manufacture technologies are considered likely to reach their limits. Such technologies notably include lithographic techniques (the so-called “top-down” approach), and such techniques may be found wanting in the future. An alternative solution may be the “bottom-up” approach (also called the self-assembly approach). In recent years, the “bottom-up” approach has yielded various nano-scaled structures, including different kinds of nanotubes and nanowires (so-called one-dimensional nano-materials). Owing to their unique structures and properties, the nano-scaled structures have shown many promising potential applications in nano-scaled electronics, photonics, sensors and superlattices. Silicon is one of the most favored materials in the semiconductor industry, and it has been used in the IC industry for many years. Therefore, silicon nanowires (SiNWs) are generally preferred over other nanowires in terms of technical compatibility. Accordingly, much attention has already been paid to the research and synthesis of silicon nanowires. As early as in 1964, Wagner et al. successfully synthesized micrometer-scaled silicon whiskers grown on silicon substrates (see Applied Physics Letters, 1964, vol. 4, p.89). Nowadays, many methods are known for synthesizing silicon nanowires, including CCVD (catalytic chemical vapor deposition), laser evaporation, direct thermal evaporation, template-directed synthesis, etc. However, most of these conventional methods have the disadvantages of producing only curled nanowires with a relative short length, and the nanowires having much impurity.
A conventional method for producing silicon nanowires has been proposed. The method includes steps of activating a vapor phase silicon monoxide or suboxide (i.e., SixO where x≧1) carried in an inert gas, and growing silicon nanowires from the activated vapor phase silicon monoxide or suboxide on a substrate maintained at a temperature ranging from 800 to 1000 degrees Celsius. However, the silicon nanowires grown by this method have random orientations with respect to the substrate. This disadvantage restricts the range of applications available for the silicon nanowires. In addition, this method produces a number of impurities. That is, a number of unwanted silicon nanoparticles having random orientations are produced, and these form a number of silicon nanoparticle chains.
Yiying Wu et al. discloses a method for growing single-crystalline Si/SiGe superlattice nanowires, in an article entitled “Block-by-Block Growth of Single-Crystalline Si/SiGe Superlattice Nanowires” (Nano Letters, Vol. 2, No. 2, p. 83-86, 2002). The method employs a substrate comprising a (111) silicon wafer coated with a thin layer of Au. The substrate is put inside a quartz tube furnace. A gas mixture containing H2 and SiCl4 is continuously introduced into the furnace. Germanium (Ge) vapor is generated in a pulsed form by pulsed ablation of a pure Ge target with a Nd:YAG laser. In this way, single-crystalline nanowires with a Si/SiGe superlattice structure are obtained.
The above article discloses a method for the synthesis of a semiconductor nanowire with periodic longitudinal heterostructures containing silicon sections and SiGe sections. However, the single-crystalline nanowires according to the above method have only one orientation; i.e., a direction perpendicular to the (111) silicon substrate. These silicon nanowires with Si/SiGe superlattices having the characteristics of only one orientation may have potential applications such as in light emitting devices. However, the method cannot be applied to produce silicon nanowire networks or other patterns, which are critical or even essential for the creation of various nano-scaled planar or three-dimensional functional structures. In addition, according to the article, the method is applied only to the (111) silicon wafer with the thin layer of Au.
Accordingly, what is needed is a method for manufacturing silicon nanowires with controlled orientations, and for manufacturing silicon nanowire arrays having controllable orientations with respect to a substrate.
An embodiment of the present invention provides a silicon nanowire structure with controllable orientations. The silicon nanowire structure comprises a substrate including a silicon wafer having a crystal plane, and a plurality of silicon nanowires extending from the substrate along a plurality of oblique epitaxial <111> directions of the substrate. The silicon nanowires are in a single crystalline form.
Preferably, the crystal plane is a (100) crystal plane, and the silicon nanowires form an angle of 35.3 degrees with respect to the (100) crystal plane.
The crystal plane can be a (110) crystal plane, and the silicon nanowires form an angle of 54.7 degrees with respect to the (110) crystal plane.
The crystal plane can be a (111) crystal plane, and accordingly the silicon nanowires form an angle of 19.4 degrees with respect to the (111) crystal plane. In addition, the silicon nanowires can grow perpendicular to the (111) crystal plane.
Another embodiment of the present invention provides a method for manufacturing a silicon nanowire structure, the method comprising:
The crystal plane comprises a (100) crystal plane, a (110) crystal plane, and a (111) crystal plane. The carrier gas comprises hydrogen gas.
The catalyst layer comprises a thin layer of a catalyst having a thickness less than 50 nanometers. Alternatively, the catalyst layer comprises a plurality of nanoparticles of a catalyst, with a diameter of the nanoparticles being less than 300 nanometers. The catalyst can be gold or iron. The silicon-containing material comprises a silicon halide, a silane and any derivative thereof, and halogenated silanes.
Other systems, methods, features, and advantages will be or become apparent to one skilled in the art upon examination of the following drawings and detailed description. It is intended that all such additional systems, methods, features, and advantages be included within this description, be within the scope of the present invention, and be protected by the accompanying claims.
Reference will now be made to the drawings to describe preferred embodiments of the present invention in detail.
According to a preferred embodiment of the present invention, self-oriented silicon nanowires can be produced by epitaxial growth on a crystalline substrate. By controlling growth conditions, controllable epitaxial growth of nanowires is realized. Therefore, mass synthesis of nanowires with controllable orientations and structure is attained, which facilitates the construction of functional nanowire devices with desired different patterns or configurations.
Substrates for growth of nanowires used in the preferred embodiments can be one of a (100) silicon wafer, a (110) silicon wafer, and a (111) silicon wafer. The (100) silicon wafer, (110) silicon wafer and (111) silicon wafer have a (100) crystal plane, a (110) crystal plane and a (111) crystal plane respectively, i.e., a surface with predefined crystal orientation. The corresponding crystal planes are used as epitaxial growth surfaces.
Prior to synthesis of silicon nanowires, the above three kinds of silicon wafers are prepared, and a catalyst thin film having a thickness on the order of nanometers is deposited on the corresponding crystal planes respectively. The catalyst thin film is preferred made of gold (Au). However, the catalyst thin film is not necessarily limited to gold, and other catalyst thin films such as one made of iron (Fe) may also be employed. The thickness of the catalyst thin film affects a diameter of silicon nanowires subsequently produced. That is, the thicker the catalyst thin film, the greater the diameter of the silicon nanowires, and vice versa. Generally, the thickness of the catalyst thin film may be in the range of several nanometers to 50 nanometers. Alternatively, a plurality of catalyst particles having diameters less than 300 nanometers may be sprinkled on the crystal planes, instead of the deposition of the catalyst thin film.
In the preferred embodiment, three large-sized silicon wafers including a (100) silicon wafer, a (110) silicon wafer, and a (111) silicon wafer coated with a gold thin film as a catalyst are first provided. Each of the large-sized silicon wafers is cut into three small pieces, each approximately 10 mm×10 mm in size. Each of the pieces is designated with a number, as shown in table 1.
In order to facilitate comparison, the preferred embodiment includes three growth runs. In each growth run, as shown in table 1, three different small pieces of silicon wafer are used for growth of silicon nanowires.
Referring initially to
It is noted that the SiCl4 liquid is used as a source of silicon. Other sources of silicon may be used instead of SiCl4 liquid. For example, a liquid comprised of derivatives of a silane, a silicon halide, halogenated silanes, etc. may be used.
The furnace 100 is heated to a reaction temperature in the range from 500 to 1100 degrees Celsius. For instance, the furnace 100 is heated to 900 degrees Celsius. Because the quartz tube 110 is longer than the furnace 100, a part (not labeled) of the quartz tube 110 inside the furnace 100 is heated to the reaction temperature, while other parts of the quartz tube 110 outside the furnace 100 remained at a relatively low temperature. The parts of the quartz tube 110 at the low temperature can be called cold parts (not labeled). Thus, a first growth run is started, and includes the following steps:
In the present embodiments, the carrier gas is not necessarily limited to the flow rates mentioned above. The flow rate of the carrier gas may be varied, so long as the carrier gas can carry enough SiCl4 vapor into the quartz tube 110 for reaction. Preferably, a molar ratio of the carried SiCl4 to the carrier gas (i.e., hydrogen) is in the range from 0.05 to 0.4; and more preferably, in the range from 0.05 to 0.2. It is understood that an amount of SiCl4 vapor carried into the quartz tube 110 for reaction can be adjusted by control of the amount of the carrier gas and the temperature of the SiCl4 vapor (i.e., the temperature of the isothermal bath). It is noted that, since a SiCl4 molecule contains only one silicon atom, the molar ratio of the SiCl4 to hydrogen equal to ratio of silicon to hydrogen; if an other material containing more than one silicon atom in a molecule is used instead of the SiCl4, the flow rate of the material may be changed according to the number of silicon atoms in the molecule of the material.
During the first growth run, a silicon layer (not shown) is deposited on an inner sidewall of the quartz tube 110. Without cleaning the silicon layer from the quartz tube 110, a second growth run is begun. Three small pieces of silicon wafers including the 21# (100) silicon wafer, the 22# (110) silicon wafer, and the 23# (111) silicon wafer are placed on the ceramic boat 116. The ceramic boat 116 is placed in the cold part of the quartz tube 110. By following the relevant steps for the first growth run described above, the second growth run is completed. After that, without cleaning the silicon layer from the quartz tube 110, a third growth run is begun. Three small pieces of silicon wafers, i.e., the 31# (100) silicon wafer, the 32# (110) silicon wafer, and the 33# (111) silicon wafer, are used for the third growth run. The same steps as for the first or second growth runs are followed.
In the above-described embodiment, the first growth run results in silicon nanowires formed on the 13# (111) silicon wafer only. No silicon nanowires are found on the 114 (100) silicon wafer or the 12# (110) silicon wafer. However, in the second growth run and the third growth run, silicon nanowires are formed on all of the silicon wafers, including the 21# (100) silicon wafer, the 22# (110) silicon wafer, and the 23# (111) silicon wafer of the second growth run, and the 31# (100) silicon wafer, the 32# (110) silicon wafer, and the 33# (111) silicon wafer of the third growth run. The silicon nanowires have a length of from approximately 10 micrometers to several tens micrometers, and a diameter of from approximately 50 nanometers to 250 nanometers.
The silicon nanowires grown on the different silicon wafers will be discussed in detailed below respectively.
Referring to
Referring to
Referring to
As described above, even though experimental conditions (including equipment, reaction temperature, reaction gases, gas flow rates, and concentrations of the reaction gases) are kept the same, the configuration of the silicon nanowires obtained in the first growth run differs from that obtained in the second and third growth runs. The reason is that concentrations of SiCl4 in a local reaction area are different in the three growth runs. Whether or not epitaxial growth occurs depends on a local concentration of silicon derived from the SiCl4 vapor. The local concentration means a concentration at an actual reaction zone where chemical reaction occurs and the silicon nanowires grow. In the first growth run, because the quartz tube 110 is freshly cleaned, a portion of the silicon derived from the SiCl4 vapor is deposited on the inner sidewall of the quartz tube 110. This results in the local concentration of silicon being relatively low. Therefore, the silicon nanowires grow only perpendicular to the silicon wafer. For the second and third growth runs, since the inner sidewall of the quartz tube 110 already has a silicon layer deposited thereon during the previous first growth run, an amount of silicon deposited on the inner sidewall gradually decreases until an equilibrium is reached. As a result, the local concentration of silicon available for reaction gradually increases to a preferred super-saturation value. Therefore, silicon nanowires grow along oblique epitaxial <111> directions.
Although the preferred embodiment includes three growth runs for comparison, the invention herein is not necessarily limited to such steps. Silicon nanowires can be grown along oblique epitaxial <111> directions so long as the local concentration of silicon reaches a preferred super-saturation value.
The above-described embodiments can control the growth directions of the silicon nanowires along oblique epitaxial <111> directions. The orientations of the silicon nanowires can be precisely controlled by the crystal orientation of the substrate. The silicon nanowires are single crystalline nanowires, and are grown along the <111> directions as confirmed by HRTEM microscopy.
The obtained silicon nanowire structures have potential applications in nanoscale photonics and/or electronic devices. For example, photonic devices can be directly implemented by patterned growth of silicon nanowires according to the embodiments without further assembling steps. In addition, it is noted that orthographic projections of the silicon nanowires on a (100) silicon wafer, a (110) silicon wafer and a (111) silicon wafer form rectangular networks, parallel straight lines, and triangular networks respectively. Thus, by directly pressing the as-synthesized silicon nanowires, planar rectangular networks, planar triangular networks or planar parallel straight line structures can be implemented. Such networks and structures can be further used in nanoelectronics.
It is believed that the present embodiments and their advantages will be understood from the foregoing description, and it will be apparent that various changes may be made thereto without departing from the spirit and scope of the invention or sacrificing all of its material advantages, the examples hereinbefore described merely being preferred or exemplary embodiments of the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 200410051311.7 | Aug 2004 | CN | national |
