KR20140112836A - Method for manufacturing a nano wire - Google Patents

Method for manufacturing a nano wire Download PDF

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KR20140112836A
KR20140112836A KR1020130027429A KR20130027429A KR20140112836A KR 20140112836 A KR20140112836 A KR 20140112836A KR 1020130027429 A KR1020130027429 A KR 1020130027429A KR 20130027429 A KR20130027429 A KR 20130027429A KR 20140112836 A KR20140112836 A KR 20140112836A
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metal
nanowire
substrate
silicon
nickel
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KR1020130027429A
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Korean (ko)
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김준동
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군산대학교산학협력단
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Publication of KR20140112836A publication Critical patent/KR20140112836A/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02603—Nanowires
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer

Abstract

The present invention is able to improve efficiency in nanowire manufacture by providing a manufacturing method for improving the growth of a nanowire from a metal silicide. A nanowire manufacturing method of the present invention comprises: a step of preparing a substrate; a step of forming a metal layer on the substrate; a step of applying Si precursors to a laminate; and a step of growing a nanowire at a temperature of 300-400°C and a pressure of 10-60 Torr.

Description

METHOD FOR MANUFACTURING A NANO WIRE BACKGROUND OF THE INVENTION [0001]

The present invention relates to a method of manufacturing a nanowire, and more particularly, to a method of manufacturing a metal silicide nanowire by synthesizing silicon and a metal.

Nanowires are linear materials with a diameter in the nanometer range and lengths of several hundred nanometers and micrometers, and the properties of the nanowires vary with diameter and length. Such a nanowire has advantages of being applicable to various kinds of fine devices due to its small size, and also it is advantageous to use the optical characteristics of electron movement and polarization phenomenon in a specific direction. In addition, nanowires are used for various applications such as lasers, transistors, memories, and sensors for chemical sensing, as materials having excellent conductivity and excellent thermal stability.

A typical method of producing nanowires is chemical vapor deposition (CVD). When a gaseous raw material gas containing a desired substance is injected into the reactor, energy is received from heat or plasma and decomposed. At this time, a desired substance reaches the substrate to form a nano-unit wire. The chemical vapor deposition method is divided into LPCVD (low pressure chemical vapor deposition), APCVD (atmospheric pressure chemical vapor deposition), and HPCVD (high pressure chemical vapor deposition) according to the pressure of the reaction chamber, and nanowires can be formed at a relatively low temperature using plasma (Plasma Enhanced Chemical Vapor Deposition), or the like.

When the nanowire is formed by the chemical vapor deposition method, the metal silicide formed by the reaction of the silicon gas and the metal layer may be formed by growing the nanowires according to the temperature and pressure conditions of the manufacturing process, The reaction proceeds in the form of a larger size and can be in the form of nanofilms.

Therefore, a manufacturing method capable of effectively manufacturing only the nanowires is required.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method of manufacturing a nanowire with improved manufacturing efficiency.

The problems of the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

According to another aspect of the present invention, there is provided a method of fabricating a nanowire including: preparing a substrate; forming a metal layer on the substrate; applying a Si precursor to the laminate; Lt; RTI ID = 0.0 > 400 C < / RTI > and a pressure in the range of 10 Torr to 60 Torr.

In one example, the nanowire manufacturing method may further include forming a protective film on the substrate after performing the step of preparing the substrate.

If the substrate has a melting point higher than the growth temperature of the nanowire, the type and composition of the substrate are not limited, but may be, for example, a semiconductor material or a metal material. In one example, the semiconductor material may comprise silicon and the metal material may be selected from the group consisting of Fe, Co, Pt, Mo, W, Y, And may include at least one selected from the group consisting of gold (Au), palladium (Pd), titanium (Ti), and nickel (Ni).

The protective film may include an oxide or nitride, and preferably silicon oxide or silicon nitride, but not limited thereto.

The metal of the metal layer may be at least one selected from the group consisting of Fe, Co, Pt, Mo, W, Y, Au, Pd, Ti, Nickel (Ni), or the like.

If the metal to be used as the metal layer is the same as the metal of the substrate, the surface of the substrate can be used as a metal catalyst layer without a separate metal layer formation process.

In addition, the Si precursor may include a reactive material containing Si and a carrier material for diluting or transporting the Si. Here, the Si-containing reactant may be a silane or a silane derivative, and the carrier may be hydrogen (H 2 ) gas or nitrogen (N 2 ) gas, but is not limited thereto.

Further, the step of growing the nanowires may be performed at a temperature in the range of 350 ° C to 400 ° C and a pressure in the range of 40 Torr to 60 Torr. More preferably at a temperature of 375 DEG C and a pressure of 50 Torr.

Meanwhile, the metal layer may be formed over the entire surface of the protective film, or may be patterned on the protective film.

In the present invention, the nanowire manufacturing method may further include a heat treatment step after the metal layer is formed.

The details of other embodiments are included in the detailed description and drawings.

The embodiments of the present invention have at least the following effects.

The manufacturing efficiency of the nanowire can be improved by providing a manufacturing method that improves the growth from the metal silicide to the nanowire.

The effects according to the present invention are not limited by the contents exemplified above, and more various effects are included in the specification.

1 is a process flow diagram of a method of manufacturing a nanowire according to an embodiment of the present invention.
FIGS. 2 and 3 are cross-sectional views of a process step of a nanowire manufacturing method according to an embodiment of the present invention.
4 is a process flow diagram of a method of manufacturing a nanowire according to another embodiment of the present invention.
FIGS. 5 to 7 are cross-sectional views of a process step of a nanowire manufacturing method according to another embodiment of the present invention.
8 is a graph showing the relationship between the temperature and the metal silicide drop size
9 is a graph showing a correlation between the drop size and the free energy of the metal silicide.
10 is a side view of the nickel silicide nanowire according to Example 1. FIG.
11 and 12 are side photographs of nickel silicide nanowires according to Comparative Example 1 and Comparative Example 2. FIG 13 is a graph showing the degree of diffusion of nickel (Ni) and silicon (Si) in the nickel silicide layer according to Example 1 to be.
14 and 15 are graphs showing the degree of diffusion of nickel (Ni) and silicon (Si) in the nickel silicide layer according to Comparative Examples 1 and 2. Fig. 16 shows the XRD spectrum of the nickel silicide layer at each temperature Graph.
17 is a front view of the nickel silicide nanowire according to Example 1. Fig.
Figs. 18 and 19 are front views of the nickel silicide nanowires according to Comparative Example 1 and Comparative Example 2. Fig.
20 to 23 are front views of nickel silicide nanowires according to Examples 2 to 3 and Comparative Examples 3 to 4 of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the accompanying drawings and embodiments. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

FIG. 1 is a process flow diagram of a method of manufacturing a nanowire according to an embodiment of the present invention, and FIGS. 2 to 3 are cross-sectional views illustrating steps of a nanowire manufacturing method according to an embodiment of the present invention.

Referring to these drawings, a method of fabricating a nanowire according to an embodiment of the present invention includes preparing a substrate 10 (S110), forming a metal layer 30 on a substrate S120, (S130) of applying a Si precursor to the laminate formed in the step (S130), and growing a nanowire (S140).

First, referring to FIG. 1, a substrate 10 is prepared (S110).

Specifically, the substrate 10 may have a melting point higher than the growth temperature of the nanowires. For example, a semiconductor material or a metal material may be used.

Preferably, the metal material is at least one selected from the group consisting of Fe, Co, Pt, Mo, Y, Y, Au, Pd, ), Nickel (Ni), or the like. When the substrate 10 is a metallic material, the conductivity of the generated nanowires may be higher than that of a semiconductor material.

Preferably, the semiconductor material may comprise silicon. Further, in one example, the substrate 10 may be a substrate entirely made of silicon, and in another example, a substrate on which a silicon layer is formed on a conductor such as an insulator or aluminum metal, such as glass, may be used . In one example, the silicon contained in the substrate 10 may have a crystalline region (not shown). The silicon can be a single crystal, polycrystalline or silicon having a microcrystalline structure. In the case of monocrystalline silicon, the single crystal itself corresponds to the crystalline region, and in the case of the polycrystalline or microcrystalline structure, the crystal grains correspond to the crystalline region. It is preferable that a single crystal structure uses silicon of a single crystal structure, which is more easy to generate metal crystal nuclei. Each crystal region of silicon may have a crystal orientation, and the nanowire may grow according to the crystal orientation of the crystal region.

Referring to FIGS. 1 and 2, a metal layer 30 is formed on a substrate 10 (S120).

The metal used for the metal layer 30 may be at least one selected from the group consisting of Fe, Co, Pt, Mo, W, Y, Au, Pd, (Ti), nickel (Ni), or the like. Preferably, the metal layer 30 may be formed of nickel (Ni). Not only does nickel have high conductivity, but nickel can also generate nanowires depending on its reactivity with silicon. Thus, the control of the reactivity of nickel and silicon may facilitate the formation of the desired nanowires.

In one example, if the metal to be used for the metal layer 30 is the same as the metal used for the substrate 10, a separate metal layer 30 forming step S120 may be omitted. That is, the surface of the substrate 10 can be used as a metal catalyst layer.

The metal layer 30 may be uniformly applied to cover the entire upper surface of the substrate 10, but may be formed on the substrate 10 with a predetermined pattern. The metal of the metal layer 30 is converted into a metal suicide drop at the interface with the crystal region so that control of the growth start point of the nanowire 40 is controlled by a pattern of the metal layer 30 formed on the substrate 10 . The size and shape of the metal pattern and the distance between each pattern are not specified, but can be adjusted in micrometers. Preferably, the size of the metal pattern for precise control of the growth start point of the nanowire 40 is 5 占 퐉 or less, the distance between the metal patterns is 3 占 퐉 or more, and the shape of the pattern may be circular or square. The thickness of the metal layer 30 to be deposited may be between 5 nm and 100 nm.

The metal pattern may be formed by a patterning method using a metal mask having an opening and a method of deactivating a part of the material layer using an ion beam, ultraviolet rays, electron beams, or the like.

Referring to FIG. 1, a Si precursor is applied to the laminate (S130).

The metal may react with the Si precursor transported into the reaction chamber to produce a metal suicide drop. The metal suicide drop may form the nanowire 40 through epitaxial growth.

The Si precursor may include a Si-containing reactive material and a transport material. Here, the Si-containing reaction material may be a silane or a silane derivative. The silane is a generic name of silicon hydride Si n H 2n + 2 , and the silane derivative is obtained by replacing hydrogen in the silane with an alkyl group, a halogen group, a hydroxyl group, or the like. For example, the Si-containing reaction material may be SiH4, SiCl4, TDMAS (Tris Dimethyimino Silane), or the like, but is not limited thereto. In addition, the carrier material may be hydrogen (H 2 ) gas or nitrogen (N 2 ) gas.

The ratio of the Si-containing reactant and the carrier material may be in the range of 1:10 to 1:40, preferably in the range of 1:20 to 1:30, in the volume ratio of Si-containing reactant: hydrogen (H 2 ) However, the present invention is not limited to these. Si-containing reactants: nitrogen (N 2) gas in a volume ratio of 1: 20 to 1: 40 may be in the range, preferably from 1: 25 to 1: 35 can be a range, it is not limited to these.

Referring to FIGS. 1 and 3, a nanowire 40 is grown (S140).

The length and thickness of the nanowire 40 can be controlled by conditions such as the temperature, pressure, reaction time, and gas inflow rate of the reaction chamber.

When the process pressure is high, the nanowire can grow in the form of a nanofilm instead of the nanowire, which is undesirable. In the case of a low pressure, the nanowire is not generated much and the density of the nanowire is low. For such reasons, a process pressure in the range of 10 Torr to 60 Torr is preferred, a process pressure in the range of 40 Torr to 60 Torr is more preferred, and most preferably 50 Torr.

The reaction time can determine the length of nanowire 40. Generally, the longer the reaction time, the longer nanowires can be generated.

Since the rate of gas entry is the rate of introduction of the Si-containing reactant that reacts with the metal, it must be injected at an appropriate rate, and the preferred rate of injection may range from 30 sccm to 50 sccm.

The process temperature is preferably in the range of 300 ° C to 400 ° C, more preferably in the range of 350 ° C to 400 ° C, and most preferably 375 ° C.

FIG. 4 is a process flow diagram of a method of manufacturing a nanowire according to another embodiment of the present invention, and FIGS. 5 to 7 are cross-sectional views illustrating steps of a nanowire manufacturing method according to another embodiment of the present invention.

Referring to these drawings, a method of manufacturing a nanowire according to another embodiment of the present invention includes a step S210 of preparing a substrate 10, a step S220 of forming a protective film 20 on the substrate 10, A step S230 of forming a metal layer 30 on the protective film 20, a step S240 of applying a Si precursor to the laminate formed in the step S230 and a step S250 of growing a nanowire .

The method of fabricating a nanowire according to another embodiment of the present invention may further include the step of forming a protective layer 20 on the substrate 10 (S220) in the method of fabricating a nanowire according to an embodiment of the present invention The remaining steps are the same. Therefore, the step of forming the protective film 20 (S220) will be described in detail below.

The protective film 20 may be formed on the substrate 10 by a method such as plasma chemical vapor deposition (PECVD), vacuum deposition, thermal oxidation, sputtering, or the like. The protective film 20 prevents the nanowire 40 from growing in a direction D2 parallel to the substrate 10 and induces the nanowire 40 to grow in a direction D1 perpendicular to the substrate 10 Can play a role. Also, the metal of the metal layer 30 can be prevented from diffusing into the substrate 10.

The substrate 10 on which the protective film 20 is formed is preferably a substrate 10 which is a semiconductor material, and a silicon substrate is more preferable.

The protective film 20 may be formed on a whole surface of the substrate 10, but may be formed on only a part of the substrate 10. For example, the protective film 20 may be selectively formed only in a region where the nanowires 40 are grown. As another example, a nanowire having growth characteristics that are different from each other can be manufactured by forming the protective film 20 on a part of the region where the nanowires are grown and forming the protective film 20 on the other part.

The protective film 20 may be formed of an oxide or nitride. For example, the protective film 20 may be formed of silicon oxide, silicon nitride, or the like.

The thickness of the protective film 20 can be adjusted within a nanosize range. For example, when silicon oxide is applied to the protective film 20, the thickness of the protective film 20 may be about 30 nm to 100 nm. In the case where silicon nitride is applied to the protective film 20, the thickness of the protective film 20 may be about 1 nm to 10 nm. In addition, the thickness of the protective film 20 may be uniform as a whole, but may be different depending on the region. In the method for fabricating a nanowire according to another embodiment of the present invention, It is preferable that the temperature of the step of growing the nanowire (S140) in the method of manufacturing nanowire according to an embodiment of the present invention is in the range of 300 ° C to 400 ° C, more preferably 350 ° C to 400 ° C And most preferably 375 ° C. A more detailed description of the process temperature is given below with reference to FIGS. 8 and 9. FIG.

FIG. 8 is a graph showing the relationship between the temperature and the metal silicide drop size, and FIG. 9 is a graph showing a correlation between the drop size and the free energy of the metal silicide.

In the growth reaction of the nanowires 40, the metal reacts with Si to form metal silicide drops, and the nanowires 40 may grow around the droplets.

The metal suicide drop may form a metal suicide layer by bonding between the drops. The thickness of the metal suicide layer may vary depending on the size of the metal suicide drop. When a metal suicide layer is formed, the reaction of the metal to the nanowire with the silicon in the air can occur above or within the formed metal suicide layer. That is, for reaction between the metal and silicon, metal and silicon must diffuse into the metal silicide layer. Since metal diffusion is generally faster than silicon, the degree of diffusion of the metal in the metal silicide layer can be an important condition for nanowire growth.

The metal silicide layer formed at an appropriate thickness facilitates the diffusion of metal and silicon to promote the reaction between the metal and silicon, thereby serving as a seed to help metal silicide grow into nanowires. Alternatively, the thickly formed metal silicide layer can interfere with the diffusion of metal and silicon, thereby inhibiting growth of the nanowires and inducing formation of nanofilms. In addition, when the thickness of the metal silicide layer is thin, the growth of the nanowire may be inhibited because it does not serve as a seed.

The thickness of the metal silicide layer is related to the process temperature.

Referring to FIG. 9, it can be seen that as the temperature increases, the size of the metal suicide drop increases. Referring to FIG. 8, there is shown a correlation between the size of the metal silicide drop and the free energy. This can be explained by the following equation.

Figure pat00001

Figure pat00002

(Note that the equation (1), and in equation 2 a and b are constants that may vary depending on the circumstances, r is the metal silicide drop size, r * is the critical size of the metal silicide drop, ΔH the enthalpy variation, γ is the interface formation energy, T is the processing temperature, T m is melting temperature, ΔG is the total free energy change, ΔGv volume is the free energy change, ΔGs refers to a surface free energy change, respectively).

Equation (1) represents a correlation between a change in total free energy (ΔG), a change in volume free energy (ΔGv), and a change in surface free energy (ΔGs) And the change (? Gv). It can be seen from Equation (2) that as the process temperature T increases, the volume free energy? Gv decreases and the decrease in the volume free energy change? Gv according to Equation (1) ) Is increased.

As shown in FIG. 8, it can be seen that the total free energy decreases as the size of the metal silicide drop becomes larger than the critical dimension r * having the maximum free energy. Therefore, a large-sized metal suicide drop produced under a high-temperature process proceeds to increase the size of the metal suicide drop so as to reduce the increased free energy change (? G). The metal silicide layer may be thickened as the size of the metal silicide drop increases, and may be in the form of a nanofilm.

On the other hand, in the case of the low-temperature process, the metal silicide drop is formed small in size. Referring to FIG. 8, a metal suicide drop having a size smaller than a metal silicide critical size r * having a maximum free energies has a smaller drop size due to random thermal fluctuations The reaction proceeds so as to be stabilized thermodynamically. Therefore, the metal silicide drop at a low temperature is reacted to become smaller, and the metal silicide layer can not be formed thick.

That is, as the temperature increases, the size of the metal suicide drop becomes larger in order to reduce the increased free energy, and grows in the form of a nanofilm. At the lower temperature, the size of the small metal suicide drop is reduced by the metal silicide drop And thus it is not effective to grow the nanowire length.

8, a rectangular region corresponds to an optimal growth region of the nanowire on the basis of the critical dimension r * of the metal silicide drop having the maximum free energy, as shown in FIG. Thus, by controlling the size of the metal suicide drop as an appropriate temperature control, a suitable metal silicide layer can be formed and the length growth to the nanowire can be induced. In one preferred example, the size of the metal suicide drop may be 300 nm or less. As disclosed in FIG. 9, the metal silicide drop in the size range can be fabricated in the range of 300 ° C to 400 ° C.

Hereinafter, the present invention will be described in more detail with reference to the following specific preparative examples and experimental examples. Those skilled in the art will not be described here because they are technically inferior enough to those skilled in the art .

Example 1

A silicon substrate was prepared as a substrate, and 500 nm of silicon oxide was deposited on the silicon substrate to form a protective film. Nickel (Ni) was formed on the protective film to a thickness of 80 nm as a metal layer. Silane (SiH 4 ) is used as the silicon-containing gas and hydrogen (H 2 ) is used as the carrier gas. The reaction chamber was fed with a total gas inlet rate of 50 sccm at a ratio of silane (SiH 4 ): hydrogen (H 2 ) = 1: 9. The total reaction time was 15 minutes, the process pressure was 50 Torr, and the temperature was 375 ° C to prepare nickel silicide nanowires.

Comparative Examples 1 and 2

A nanowire was prepared in the same manner as in Example 1, except that the process temperature of the reaction chamber was changed to 250 ° C (Comparative Example 1) and 500 ° C (Comparative Example 2).

Experimental Example 1: Thickness of layer of nickel suicide

The nickel suicide nanowires according to Example 1 and Comparative Examples 1 and 2 were side-taken by cross-sectional SEM to measure the thickness of the nickel suicide layer. The results are shown in Table 1 and Example 1, in FIG. 10, and in Comparative Example 1, Fig. 11 and Comparative Example 2 are shown in Fig. 12, respectively.

Process temperature The thickness of the nickel suicide layer Example 1 375 DEG C 206 nm Comparative Example 1 250 ℃ 94 nm Comparative Example 2 500 ℃ 629 nm

Referring to Table 1 and FIG. 10, FIG. 11, and FIG. 12, it can be seen that the thickness of the nickel silicide layer varies with the process temperature.

Referring to Table 1 and FIGS. 10 to 12, it can be seen that the thickness of the nickel silicide layer formed according to the temperature is changed. When the temperature was 375 ° C, the nickel silicide layer was formed at 206 nm. When the temperature was 250 ° C, the nickel silicide layer was measured at 94 nm. When the temperature was 500 ° C, the silicide layer had a thickness of 629 nm . ≪ / RTI > This is related to the size of the nickel suicide drop according to the temperature described above. That is, the nickel suicide drop was formed at a high temperature of 500 ° C. and grown as a nanofilm. At a low temperature of 250 ° C., the nickel suicide drop was small and the nickel silicide layer was not formed properly.

Experimental Example 2: Spread of nickel (Ni) and silicon (Si)

The degree of diffusion of nickel (Ni) and silicon (Si) according to Example 1 and Comparative Examples 1 and 2 was measured. The results are shown in Fig. 13, Comparative Example 1, and Comparative Example 2, Respectively.

Referring to FIGS. 13 to 15 together with FIG. 16, the degree of diffusion of nickel and silicon according to the thickness of the nickel silicide will be examined. 16 is the XRD spectrum on nickel silicide at the temperature of each example.

First, as shown in FIG. 13, when the process temperature is 375 ° C., it can be seen that nickel and silicon are uniformly distributed within the thickness range of the nickel silicide layer. Referring to the 375 캜 spectrum of FIG. 16, it can be seen that the peaks of NiSi 2 , NiSi and Ni 3 Si 2 are distinct. That is, it can be seen that nickel silicide formation is formed by NiSi 2 , NiSi, and Ni 3 Si 2 , which is advantageous for nanowire growth because nickel and silicon are uniformly distributed in the nickel silicide layer.

As shown in FIG. 14, at a low temperature of 250 ° C., it can be seen that the content of nickel is maintained at a high content and the content of silicon is small in the thickness range of the nickel silicide layer. However, it can be seen that the content of nickel is decreased and the content of silicon is increased in the upper surface portion, which is a result of the reaction according to the supply of the external silane. Therefore, it can be confirmed that the diffusion of nickel and silicon is not performed properly inside. Referring to the 250 ° C spectrum of FIG. 16, it can be seen that peaks of Ni and Ni 3 Si, which are excessive nickel, are apparent due to the content ratio of the nickel silicide layer.

As shown in FIG. 15, at a high temperature of 500 ° C., the content of nickel is excessively reduced in the thickness range of the nickel silicide layer compared with that of silicon. Particularly, in the upper layer portion, the content of nickel is too small compared to silicon. Referring to the 500 캜 spectrum of FIG. 16, it can be seen that NiSi 2 peak showing an excess of silicon appears due to the content ratio of the nickel silicide layer.

Experimental Example 3: Generation of nanowires

The nanowires produced according to Example 1 and Comparative Examples 1 and 2 were photographed frontally by FESEM (Field Emission Scanning Electron Microscope). The results are shown in Fig. 17 in Example 1, Fig. 18 in Comparative Example 1, 19, respectively.

As shown in FIG. 17, it can be seen that the nickel silicide layer functions as a seed at 375 ° C., and the nanowire is produced at a high density. As shown in FIG. 18, at 250 ° C., nickel suicide The nanowires are not formed much because the layer is thin, and as shown in FIG. 19, it can be confirmed that the nickel silicide layer is too thick at 500 ° C. to form the nanofilm.

Thus, it can be seen that the process temperature of 375 ° C in Example 1 corresponds to a suitable process temperature for controlling the size of the nickel suicide drop to correspond to the critical size (r *) region shown in FIG.

Examples 2 and 3

A silicon substrate was prepared as a substrate, and 500 nm of silicon oxide was deposited on the silicon substrate to form a protective film. Nickel (Ni) was formed on the protective film to a thickness of 80 nm as a metal layer. Silane (SiH 4 ) is used as the silicon-containing gas, and hydrogen (H 2 ) is used as the carrier gas. (SiH 4 ): hydrogen (H 2 ) = 1: 9 at a total gas inlet rate of 50 sccm. The total reaction time was 15 minutes, the reaction temperature was 400 占 폚, the pressure was 10 Torr (Example 2) and 50 Torr (Example 3) to prepare nickel silicide nanowires.

Comparative Examples 3 to 4

A nanowire was prepared in the same manner as in Example 2, except that the process pressure of the reaction chamber was changed to 75 Torr (Comparative Example 3) and 100 Torr (Comparative Example 4).

Figs. 20 to 23 show front views of the nickel silicide nanowires according to Examples 2 to 3 and Comparative Examples 3 to 4, respectively.

Experimental Example 1: Measurement of density of nanowires

The density of the nickel silicide nanowires according to Examples 2 to 3 and Comparative Examples 3 to 4 was measured and the results are shown in Table 2 below.

Process pressure Nanowire density Example 2 10 Torr 7.1 × 10 7 / cm 2 Example 3 50 Torr 15.7 × 10 7 / cm 2 Comparative Example 3 75 Torr 1.97 × 10 7 / cm 2 Comparative Example 4 100 Torr 1.7 × 10 7 / cm 2

Referring to Table 2, when the process pressure is 50 Torr, the nanowire density is as high as 15.7 × 10 7 / cm 2 , and when the process pressure is 10 Torr, the nanowire density is maintained at half the level of 50 Torr Can be confirmed. On the other hand, as the pressure increases to 75 Torr and 100 Torr, the density of nanowires decreases by about 1/10 as compared with 50 Torr at 1.97 × 10 7 / cm 2 and 1.7 × 10 7 / cm 2 . Therefore, the optimum pressure of the nanowire production process is 10 Torr to 60 Torr, preferably 50 Torr. This is presumably due to the correlation between the pressure and the size of the nickel silicide. Therefore, it can be seen that the pressure of 50 Torr corresponds to a proper process pressure for controlling the size of the nickel suicide drop to correspond to the critical dimension (r *) region shown in FIG.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It can be understood that It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

10: substrate 20: protective film
30: metal layer 40: nanowire

Claims (15)

Preparing a substrate;
Forming a metal layer on the substrate;
Applying a Si precursor to the laminate; And
Growing the nanowires at a temperature in the range of 300 ° C to 400 ° C and a pressure in the range of 10 Torr to 60 Torr;
≪ / RTI > The method according to claim 1,
After the step of preparing the substrate,
And forming a protective film on the substrate. The method according to claim 1,
Wherein the substrate is a semiconductor material or a metal material. The method of claim 3,
The metal material may be at least one selected from the group consisting of Fe, Co, Pt, Mo, W, Y, Au, Pd, 0.0 > (Ni). ≪ / RTI > The method of claim 3,
Wherein the semiconductor material comprises silicon. 3. The method of claim 2,
Wherein the protective film is an oxide or a nitride. The method according to claim 6,
Wherein the protective film is silicon oxide or silicon nitride. The method according to claim 1,
The metal of the metal layer may be at least one selected from the group consisting of Fe, Co, Pt, Mo, W, Y, Au, Pd, Ti, And nickel (Ni). The method according to claim 1,
Wherein the Si precursor comprises a Si-containing reactive material and a carrier material. 10. The method of claim 9,
Wherein the Si-containing reaction material is a silane or a silane derivative. 11. The method of claim 10,
Wherein the Si-containing reaction material is at least one selected from the group consisting of SiH 4 , SiCl 4, and TDMAS. 10. The method of claim 9,
The transfer material The method for producing hydrogen (H 2) gas or nitrogen (N 2) gas of the nanowire. The method according to claim 1,
Wherein the step of growing the nanowire is performed at a temperature in the range of 350 ° C to 400 ° C and a pressure in the range of 40 Torr to 60 Torr. 3. The method according to claim 1 or 2,
Wherein the metal layer is formed on the substrate or the protective film by patterning. The method according to claim 1,
Further comprising the step of heat treating the metal layer.
KR1020130027429A 2013-03-14 2013-03-14 Method for manufacturing a nano wire KR20140112836A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016171487A1 (en) * 2015-04-22 2016-10-27 성균관대학교산학협력단 Nano-wire solar cell and manufacturing method therefor
CN113433144A (en) * 2021-06-23 2021-09-24 大连交通大学 Method for researching growth mechanism of platinum nanowire crystal face on different mesoporous metal oxide crystal faces

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016171487A1 (en) * 2015-04-22 2016-10-27 성균관대학교산학협력단 Nano-wire solar cell and manufacturing method therefor
CN113433144A (en) * 2021-06-23 2021-09-24 大连交通大学 Method for researching growth mechanism of platinum nanowire crystal face on different mesoporous metal oxide crystal faces
CN113433144B (en) * 2021-06-23 2024-01-30 大连交通大学 Method for researching growth mechanism of platinum nanowire crystal face on different mesoporous metal oxide crystal faces

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