JP2012056015A - Method for manufacturing nanowire device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a nanowire device allowing for excellent degree of freedom in the aspects of semiconductor connection and commercial product designing.SOLUTION: The method includes: forming a plurality of nanowire-shaped semiconductors 2 on the surface of a semiconductor substrate 1 by growing a crystal epitaxially; filling a filler 5 into a gap of the nanowire-shaped semiconductors 2 to bury the nanowire-shaped semiconductor 2 so as to form a nanowire-shaped semiconductor-filler composite 6; and peeling the nanowire-shaped semiconductor-filler composite 6 from the semiconductor substrate to form nanowire-shaped semiconductor arrays 9, 10, 11, 13, 14 and 15. The peeling of the nanowire-shaped semiconductor-filler composite 6 is performed by external force after forming a support substrate 8 on the filler 5; or the support substrate 8 is formed on the filler 5 after peeling the nanowire-shaped semiconductor-filler composite 6 by thermal contraction stress of the filler 5.

Description

  The present invention relates to a method for manufacturing a nanowire device.

  In recent years, a nanowire-like semiconductor array is known in which a plurality of nanowire-like semiconductors are formed by epitaxially growing crystals substantially vertically on the surface of a semiconductor substrate (see, for example, Non-Patent Document 1). Applications of the nanowire-like semiconductor array as devices such as solar cells, light-emitting devices, transistors, and various sensors are being studied. In the present application, a device including the nanowire-like semiconductor array is referred to as a “nanowire device”.

Junichi Motohisa, Takashi Fukui, “Semiconductor nanowires and nanodevice applications”, Applied Physics, Vol. 75, No. 3, 2006, pp. 296-302

  However, since the conventional nanowire device forms a nanowire-like semiconductor on the surface of the semiconductor substrate during manufacture, the semiconductor substrate becomes a support substrate as it is, and there is a disadvantage that it is restricted in terms of semiconductor bonding and product design. is there.

  An object of the present invention is to provide a method for manufacturing a nanowire device that can eliminate such disadvantages and can obtain a high degree of freedom in terms of semiconductor bonding and product design.

  In order to achieve such an object, a first aspect of a method for producing a nanowire device of the present invention includes a step of epitaxially growing a crystal on a surface of a semiconductor substrate to form a plurality of nanowire-like semiconductors, Filling the gap with a filler and embedding the nanowire-like semiconductor to form a nanowire-like semiconductor-filler composite, and supporting the nanowire-like semiconductor-filler composite on the surface opposite to the semiconductor substrate A step of forming a substrate, and the nanowire-like semiconductor-filler composite is peeled from the semiconductor substrate by an external force to form a nanowire-like semiconductor array including the nanowire-like semiconductor-filler composite and the support substrate. And a process.

  According to the first aspect of the present invention, first, a nanowire-like semiconductor is embedded by filling a gap between a plurality of nanowire-like semiconductors formed by epitaxially growing crystals on the surface of a semiconductor substrate. A semiconductor-filler composite is formed. Next, a support substrate is formed on the surface of the nanowire-like semiconductor-filler composite opposite to the semiconductor substrate, and the nanowire-like semiconductor-filler composite is peeled from the semiconductor substrate by an external force.

  As a result, a nanowire semiconductor array including the nanowire semiconductor-filler composite and the support substrate can be formed, and the nanowire semiconductor array can be used as a nanowire device. Since the nanowire device obtained by the first aspect of the present invention forms a support substrate different from the semiconductor substrate in the nanowire-like semiconductor-filler composite, a desired material can be used as the support substrate, Excellent flexibility in terms of semiconductor bonding and product design can be obtained.

  Further, in the first aspect of the method for producing a nanowire device of the present invention, after the nanowire-like semiconductor is filled by filling a gap in the nanowire-like semiconductor to form the nanowire-like semiconductor-filler composite, Removing a part of the filler opposite to the semiconductor substrate to expose the tip of the nanowire-like semiconductor; and forming an electrode connected to the exposed tip of the nanowire-like semiconductor; And a step of forming the support substrate on the electrode.

  By doing so, in the first aspect of the present invention, an electrode made of a desired material can be interposed between the nanowire-like semiconductor-filler composite and the support substrate.

  On the other hand, the second aspect of the method for producing a nanowire device of the present invention includes a step of epitaxially growing a crystal on the surface of a semiconductor substrate to form a plurality of nanowire-like semiconductors, and filling a gap between the nanowire-like semiconductors. The nanowire-like semiconductor is embedded to form a nanowire-like semiconductor-filler composite, and the filler is thermally shrunk from the semiconductor substrate by the heat shrinkage stress of the filler. Peeling the filler complex to form a nanowire semiconductor array comprising the nanowire semiconductor-filler complex.

  According to the second aspect of the present invention, first, a nanowire-like semiconductor is embedded by filling a gap between a plurality of nanowire-like semiconductors formed by epitaxially growing crystals on the surface of a semiconductor substrate. A semiconductor-filler composite is formed. Next, the filler is thermally contracted, and the nanowire-like semiconductor-filler composite is peeled from the semiconductor substrate by the thermal contraction stress of the filler.

  As a result, a nanowire semiconductor array made of the nanowire semiconductor-filler composite can be formed, and the nanowire semiconductor array can be used as a nanowire device. According to the second aspect of the present invention, since the nanowire-like semiconductor-filler composite is peeled from the semiconductor substrate by the heat shrinkage stress of the filler, the filler may be heat-shrinked. There is no need to apply an external force to the semiconductor-filler composite. Therefore, the operation of peeling the nanowire-like semiconductor-filler composite from the semiconductor substrate can be easily performed.

  Further, in the second aspect of the method for producing a nanowire device of the present invention, after the nanowire-like semiconductor is filled by filling a gap in the nanowire-like semiconductor to form the nanowire-like semiconductor-filler composite, And a step of forming a heat-shrinkable material layer on the surface of the nanowire-like semiconductor-filler composite opposite to the semiconductor substrate.

  Thus, in the second aspect of the present invention, when the filler is thermally shrunk and the nanowire-like semiconductor-filler composite is peeled from the semiconductor substrate, the heat-shrinkable material layer is also Heat shrinkable. Therefore, in addition to the heat shrinkage stress of the filler, the heat shrinkage stress of the heat-shrinkable material layer can also act, and the operation of peeling the nanowire-like semiconductor-filler composite from the semiconductor substrate is easier. Can be done.

  Further, in the second aspect of the method for producing a nanowire device of the present invention, after the nanowire-like semiconductor is filled by filling a gap in the nanowire-like semiconductor to form the nanowire-like semiconductor-filler composite, Removing a part of the filler on the side opposite to the semiconductor substrate to expose the tip of the nanowire-like semiconductor, and forming an electrode connected to the exposed tip of the nanowire-like semiconductor, Forming a nanowire-like semiconductor-filler composite comprising an electrode.

  By doing in this way, in the 2nd aspect of this invention, the electrode which consists of desired materials can be provided in the said nanowire-like semiconductor-filler composite_body | complex. The electrode may be made of a heat-shrinkable material. In this case, the heat-shrinkable material layer is formed on the surface opposite to the semiconductor substrate of the nanowire-like semiconductor-filler composite. The same effect can be achieved.

  On the other hand, when the electrode is not a heat-shrinkable material, the second aspect of the method for producing a nanowire device of the present invention preferably includes a step of forming a heat-shrinkable material layer on the electrode. Thus, in the second aspect of the present invention, even when an electrode that is not a heat-shrinkable material is formed, the nanowire-like semiconductor-filler composite is provided on the surface opposite to the semiconductor substrate. The same effect as when the heat-shrinkable material layer is formed can be obtained.

  Moreover, it is preferable that the 2nd aspect of the manufacturing method of the nanowire device of this invention comprises the process of forming a support substrate in the outermost layer of the said nanowire-like semiconductor array.

  In the nanowire device obtained by the second aspect of the present invention, a support substrate different from the semiconductor substrate can be formed on the nanowire-like semiconductor-filler composite by forming the support substrate. Therefore, a desired material can be used as the support substrate, and an excellent degree of freedom in terms of semiconductor bonding and product design can be obtained.

  The support substrate may be provided on the opposite side of the surface of the nanowire-like semiconductor-filler composite that is peeled from the semiconductor substrate, or may be provided on the surface that is peeled from the semiconductor substrate.

  The support substrate may be formed on the heat-shrinkable material layer when the nanowire-like semiconductor-filler composite includes only the heat-shrinkable material layer or the electrode and the heat-shrinkable material layer. It may be provided. Furthermore, the support substrate may be provided on the electrode when the nanowire-shaped semiconductor-filler composite includes only the electrode.

  The method of manufacturing a nanowire device of the present invention may include, in any one of the above aspects, a step of epitaxially growing a crystal made of a material different from the semiconductor substrate to form a plurality of nanowire semiconductors on the surface of the semiconductor substrate. preferable. By doing so, the semiconductor substrate and the nanowire-like semiconductor are heterojunctioned, and a strain is formed between them, so that the nanowire-like semiconductor-filler composite is peeled from the semiconductor substrate. This operation can be performed more easily.

  Further, in any of the above-described methods for producing a nanowire device of the present invention, a part of the surface of the semiconductor substrate is covered with an amorphous film, and the surface of the semiconductor substrate exposed from the amorphous film Furthermore, the nanowire-like semiconductor can be formed by providing a step of epitaxially growing a crystal to form a plurality of nanowire-like semiconductors.

  In this case, in the method for manufacturing a nanowire device according to the present invention, the diameter of the surface of the semiconductor substrate exposed from the amorphous film is preferably smaller than the diameter of the nanowire-like semiconductor. By doing so, strain is formed between the semiconductor substrate and the nanowire-like semiconductor, so that the operation of peeling the nanowire-like semiconductor-filler composite from the semiconductor substrate can be further easily performed. it can.

  Also, the method for producing a nanowire device of the present invention includes a step of arranging a catalytic metal on the surface of the semiconductor substrate and epitaxially growing a crystal through the catalytic metal to form a plurality of nanowire-like semiconductors. The nanowire-like semiconductor can be formed.

  The nanowire device manufacturing method of the present invention, in any one of the above aspects, forms a plurality of nanowire-like semiconductors by epitaxially growing crystals on the surface of the semiconductor substrate from which the nanowire-like semiconductor-filler composite has been peeled off. It is preferable to do. By doing in this way, in the manufacturing method of the nanowire device of the present invention, the semiconductor substrate can be reused.

  The reuse of the semiconductor substrate is particularly advantageous when the semiconductor substrate itself is expensive or when a complicated treatment is required to cover a part of the surface of the semiconductor substrate with the amorphous film. It is.

Explanatory sectional drawing which shows the 1st form of the manufacturing method of this invention. FIG. 2 is a plan view showing the configuration of the semiconductor substrate shown in FIG. 1. The scanning electron micrograph of the semiconductor substrate corresponding to FIG. The scanning electron micrograph of the nanowire-like semiconductor formed in the semiconductor substrate. The scanning electron micrograph of the nanowire-like semiconductor array peeled from the semiconductor substrate. The scanning electron micrograph of the semiconductor substrate after the nanowire-like semiconductor array is peeled off. The scanning electron micrograph of the nanowire-like semiconductor formed in the reused semiconductor substrate. Explanatory sectional drawing which shows the 2nd form of the manufacturing method of this invention. Explanatory sectional drawing which shows the 3rd form of the manufacturing method of this invention. Explanatory sectional drawing which shows the 4th form of the manufacturing method of this invention.

  Next, embodiments of the present invention will be described in more detail with reference to the accompanying drawings.

  Next, with reference to FIG.1 and FIG.2, the manufacturing method of the nanowire device of the 1st Embodiment of this invention is demonstrated.

  As shown in FIG. 1A, in the manufacturing method of the nanowire device according to the first embodiment of the present invention, first, a crystal made of the same material as that of the semiconductor substrate 1 is epitaxially grown on the surface of the semiconductor substrate 1 to obtain a plurality of The nanowire semiconductor 2 is formed.

  As the semiconductor substrate 1, for example, a semiconductor substrate such as Ge, Si, InP, GaAs, InAs, GaP, AlAs, InSb, GaSb, GaN, InN, AlN, 3C—SiC, 6H—SiC, or ZnSe is used. Can do.

  As shown in FIG. 2, a part of the surface of the semiconductor substrate 1 is covered with an amorphous film 4 having circular holes 3 arranged in a triangular lattice pattern, and the surface of the semiconductor substrate 1 is formed from the circular holes 3. Exposed. A nanowire semiconductor 2 shown in FIG. 1A is formed in a circular hole 3.

The nanowire semiconductor 2 can be formed as follows, for example. First, the InP (111) A semiconductor substrate 1 is cleaned, and an amorphous SiO ₂ film 4 is formed to a thickness of about 20 nm on the surface of the InP (111) A semiconductor substrate 1 using an RF sputtering apparatus equipped with a SiO ₂ target. The film is formed.

Next, a positive resist is applied on the amorphous SiO ₂ film 4, the InP (111) A semiconductor substrate 1 is set in an electron beam drawing apparatus, and a pattern is drawn on the positive resist. In the pattern, for example, as shown in FIG. 2, circular holes 3 having a diameter of 100 nm are arranged in a triangular lattice pattern at a pitch of 400 nm.

After the drawing, the resist is developed, the InP (111) A semiconductor substrate 1 is immersed in a 10% -BHF solution, and SiO ₂ in the circular holes 3 is removed by etching. Then, after the etching, the resist is removed. A scanning electron micrograph (50000 times) corresponding to FIG. 2 of the obtained InP (111) A semiconductor substrate 1 is shown in FIG.

Next, the InP (111) A semiconductor substrate 1 on which the amorphous SiO ₂ film 4 is formed is set in a MOVPE apparatus, and the chamber is evacuated and then replaced with H ₂ gas. The total pressure is stable at 0.1 atm. Adjust the flow rate and exhaust speed so that Next, the substrate temperature reaches 660 ° C. while flowing a mixed gas (total pressure: 0.1 atm, TBP partial pressure: 1.1 × 10 ⁻⁴ atm) of TBP (tertialybutylphosphine) and carrier gas (H ₂ ). The temperature rises to

Next, after the substrate temperature reaches 660 ° C., the flowing gas is switched to a mixed gas of TMI (trimetylindium), TBP, and carrier gas, the mixed gas is introduced into the reaction chamber, and the nanowire-like InP semiconductor 2 is epitaxially grown. Let The total pressure remains at 0.1 atm, and the flow rate of each organometallic gas is adjusted so that the partial pressure of TMI is 4.4 × 10 ⁻⁶ atm and the partial pressure of TBP is 5.5 × 10 ⁻⁵ atm. .

After 20 minutes, the flow gas is switched to a mixed gas of TBP and carrier gas (total pressure: 0.1 atm, TBP partial pressure: 1.1 × 10 ⁻⁴ atm), and the epitaxial growth of the p-type InP semiconductor 2 is completed. Next, the InP (111) A semiconductor substrate 1 is taken out by cooling with the mixed gas of TBP and carrier gas flowing.

  A scanning electron micrograph (magnified 30000 times) of the nanowire-like semiconductor 2 formed on the InP (111) A semiconductor substrate 1 is shown in FIG. The nanowire-like semiconductor 2 thus formed has a height of 3000 nm and a diameter of 180 nm, for example.

Next, as shown in FIG. 1 (b), a filler 5 is filled in the gap between the nanowire semiconductors 2, the nanowire semiconductor 2 is embedded in the filler 5, and the nanowire semiconductor-filler composite 6 is formed. Form. Examples of the filler 5 include BCB resin (divinyltetramethylsiloxane benzocyclobutene resin, manufactured by Dow Chemical Company, trade name: Cycloten 3022-35), SiO ₂ , SiOF, Si—H containing SiO ₂ , SiOC, methyl Group-containing SiO ₂ , polyimide polymer film, paraxylylene polymer film, fluorine-doped amorphous carbon, aromatic hydrocarbon polymer, polyallyl ether material, silica glass, phenol resin, epoxy resin, melamine resin, Urea resin, unsaturated polyester resin, alkyd resin, polyurethane, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polytetrafluoroethylene, acrylonitrile butadiene styrene resin, acrylonitrile-styrene copolymer resin, acrylic resin Polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, polyethylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polysulfone, polyether sulfone, amorphous polymer, polyether ether ketone, thermoplastic polyimide, polyamide amide, acrylic rubber, Nitrile rubber, isoprene rubber, urethane rubber, ethylene propylene rubber, epichlorohydrin rubber, chloroprene rubber, silicone rubber, styrene / butadiene rubber, butadiene rubber, fluorine rubber, polyisobutylene, and the like can be used.

  When the BCB resin is used as the filler 5, for example, spin coating is applied to fill the gaps between the nanowire-like semiconductors 2, and then annealing is performed in an inert gas atmosphere at a temperature of, for example, 250 ° C. for 1 hour. It can be cured by doing so.

Next, as shown in FIG. 1C, a part of the filler 5 on the side opposite to the semiconductor substrate 1 is removed to expose the tip of the nanowire-like semiconductor 2. For example, when the filler 5 is the BCB resin, a part of the filler 5 is removed by a reactive ion etching (RIE) process using a mixed gas of CF ₄ and O ₂ . This can be done by etching the BCB resin. As a result, the tip of the nanowire semiconductor 2 is exposed, for example, by 150 nm.

  Next, as shown in FIG. 1D, an electrode 7 connected to the exposed tip of the nanowire-like semiconductor 2 is formed. The electrode 7 can be formed of, for example, ITO. The electrode 7 made of ITO can be formed using, for example, an RF sputtering apparatus equipped with an ITO target.

Next, as shown in FIG.1 (e), the support substrate 8 is formed on the electrode 7 currently formed in the surface on the opposite side to the semiconductor substrate 1 of the nanowire-like semiconductor-filler composite body 6. FIG. As the support substrate _8, it can be used SiO 2, InP, GaAs, InAs , GaP, AlAs, one made of GaSb, and the like. For example, when the support substrate 8 is made of SiO ₂ , the support substrate 8 can be formed on the electrode 7 by adhering to the electrode 7 using a conductive carbon double-sided adhesive tape.

  Next, as shown in FIG. 1 (e), an external force acting in a direction to separate the semiconductor substrate 1 and the nanowire-like semiconductor-filler composite 6 is applied to the semiconductor substrate 1 and the nanowire-like semiconductor-filler composite 6. The agent complex 6 is peeled off. As a result, as shown in FIG. 1 (f), a nanowire-like semiconductor array 9 in which the electrode 7 is interposed between the nanowire-like semiconductor-filler composite 6 and the support substrate 8 can be obtained.

  Scanning electron micrographs of the resulting nanowire-like semiconductor array 9 are shown in FIGS. 5 (a) and 5 (b). 5A is 15000 times, and FIG. 5B is 50000 times. FIG. 5A shows the electrode 7 as an ITO layer.

Next, the semiconductor substrate 1 from which the nanowire-like semiconductor array 9 has been peeled is subjected to ultrasonic cleaning. The ultrasonic cleaning may be performed using any general-purpose ultrasonic cleaning apparatus. For example, the ultrasonic cleaning has a frequency in the range of 20 to 100 kHz and an intensity of 0.5 to ¹⁰ W / cm ^2. Can be used. The ultrasonic cleaning can be carried out in this range of frequencies and intensities for 20 minutes in butanol, 10 minutes in isopropanol, 10 minutes in ethanol, and in that order, followed by 20 minutes in ultrapure water. .

  Scanning electron micrographs of the semiconductor substrate 1 after the nanowire-like semiconductor array 9 is peeled off and cleaned by the ultrasonic cleaning are shown in FIGS. 6 (a) and 6 (b). 6A is 70000 times, and FIG. 6B is 200000 times.

  The semiconductor substrate 1 ultrasonically cleaned as described above can be reused for forming the nanowire-like semiconductor 2. Next, FIG. 7 shows a scanning electron micrograph (30000 times) of the nanowire-like semiconductor 2 formed on the semiconductor substrate 1 after the ultrasonic cleaning in exactly the same manner as described above. From FIG. 7, the nanowire-like semiconductor 2 formed on the reused semiconductor substrate 1 has no inferiority to the nanowire-like semiconductor 2 shown in FIG. 4 formed on the virgin semiconductor substrate 1. It is clear that it can be used.

  In the manufacturing method of the first embodiment shown in FIG. 1, the steps shown in FIGS. 1C and 1D are omitted, and the semiconductor of the nanowire-like semiconductor-filler composite 6 shown in FIG. The support substrate 8 may be directly formed on the surface opposite to the substrate 1. In this case, as shown in FIG. 1G, a nanowire-like semiconductor array 10 composed of the nanowire-like semiconductor-filler composite 6 and the support substrate 8 can be obtained.

  Next, with reference to FIG. 8, the manufacturing method of the nanowire device of the 2nd Embodiment of this invention is demonstrated.

  As shown in FIG. 8A, in the method of manufacturing a nanowire device according to the second embodiment of the present invention, first, a crystal made of the same material as that of the semiconductor substrate 1 is epitaxially grown on the surface of the semiconductor substrate 1 to obtain a plurality of The nanowire semiconductor 2 is formed.

  As the semiconductor substrate 1, for example, a semiconductor substrate such as Ge, Si, InP, GaAs, InAs, GaP, AlAs, InSb, GaSb, GaN, InN, AlN, 3C—SiC, 6H—SiC, or the like can be used. . The semiconductor has a linear expansion coefficient in the range of 2.6 to 6.7 ppm / ° C.

  The nanowire semiconductor 2 can be formed in the same manner as in the first embodiment shown in FIG. InP has a linear expansion coefficient (thermal contraction rate) of 4.5 ppm / ° C.

  Next, as shown in FIG. 8B, the gap between the nanowire-like semiconductors 2 is filled with the filler 5, the nanowire-like semiconductor 2 is embedded in the filler 5, and the nanowire-like semiconductor-filler composite 6 is formed. Form.

Examples of the filler 5 include BCB resin (divinyltetramethylsiloxane benzocyclobutene resin, manufactured by Dow Chemical Company, trade name: Cycloten 3022-35), SiO ₂ , SiOF, Si—H containing SiO ₂ , SiOC, methyl Group-containing SiO ₂ , polyimide polymer film, paraxylylene polymer film, tetrafluoroethylene polymer film, fluorine-doped amorphous carbon, aromatic hydrocarbon polymer, polyallyl ether material, silica glass, phenol Resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, polyethylene terephthalate, cyclic polyolefin, polypheny Nsurufaido can polysulfone, polyether sulfone, amorphous polymers, polyetheretherketone, thermoplastic polyimide, the use of polyamide amides.

  When the BCB resin is used as the filler 5, for example, spin coating is applied to fill the gaps between the nanowire-like semiconductors 2, and then annealing is performed in an inert gas atmosphere at a temperature of, for example, 250 ° C. for 1 hour. It can be cured by doing so. The BCB resin has a linear expansion coefficient (thermal contraction rate) of 52.0 ppm / ° C.

  Next, the semiconductor substrate 1 and the nanowire-like semiconductor-filler composite 6 are heated, and the filler 5 is thermally contracted. In this case, the BCB resin as the filler 5 has a larger linear expansion coefficient (thermal contraction rate) than InP as the semiconductor substrate 1, and therefore, as shown in FIG. The part where the agent composite 6 is separated from the semiconductor substrate 1 contracts more greatly. As a result, the nanowire-like semiconductor-filler composite 6 is peeled from the semiconductor substrate 1.

  The operation of thermally shrinking the filler 5 includes, for example, heating the semiconductor substrate 1 and the nanowire-like semiconductor-filler composite 6 to 400 ° C. in a nitrogen stream, holding the temperature at 400 ° C. for 5 minutes, and then to room temperature. This can be done by cooling.

Next, as shown in FIG. 8D, the nanowire semiconductor-filler composite 6 is formed by forming a support substrate 8 on the surface opposite to the peeling surface 6 a of the nanowire semiconductor-filler composite 6. Thus, a nanowire-like semiconductor array 11 comprising the support substrate 8 can be obtained. As the support substrate 8, the same material as that in the first embodiment shown in FIG. For example, when the support substrate 8 is made of SiO ₂ , the support substrate 8 can be formed on the nanowire-like semiconductor-filler composite 6 by adhering to the filler 5 using a conductive carbon double-sided adhesive tape.

  Next, with reference to FIG. 9, the manufacturing method of the nanowire device of the 3rd Embodiment of this invention is demonstrated.

  As shown in FIG. 9A, in the method of manufacturing a nanowire device according to the third embodiment of the present invention, first, a crystal made of the same material as that of the semiconductor substrate 1 is epitaxially grown on the surface of the semiconductor substrate 1 to obtain a plurality of The nanowire semiconductor 2 is formed.

  As the semiconductor substrate 1, for example, a substrate made of the same semiconductor as in the second embodiment shown in FIG. 8A can be used, and the nanowire-like semiconductor 2 is the first semiconductor shown in FIG. It can be formed in the same manner as in the embodiment.

  Next, as shown in FIG. 9B, the gap between the nanowire semiconductors 2 is filled with the filler 5, the nanowire semiconductors 2 are embedded in the filler 5, and the nanowire semiconductor-filler composite 6 is formed. Form. As the filler 5, the same material as that in the second embodiment shown in FIG. 8B can be used.

  Next, as shown in FIG. 9C, a heat-shrinkable material layer 12 is formed on the surface of the nanowire-like semiconductor-filler composite 6 opposite to the semiconductor substrate 1. The heat-shrinkable material layer 12 can be formed as a film made of a metal such as Ag, Al, Mn, Zn, Au, or Ti. The metal has a linear expansion coefficient (thermal contraction rate) in the range of 10 to 31 ppm / ° C. The heat-shrinkable material layer 12 may be a coating made of any one of the metals, or may be a coating combining two or more of the metals such as a Ti / Au metal multilayer film.

  The heat-shrinkable material layer 12 made of a Ti / Au metal multilayer film can be formed as follows, for example. First, the nanowire-like semiconductor-filler composite 6 with the tip of the nanowire-like semiconductor 2 exposed by 150 nm is attached to a vacuum deposition apparatus by reactive ion etching (RIE) processing. Next, after evacuating the sample chamber of the vacuum vapor deposition apparatus, a Ti film having a thickness of 500 mm is formed by electron beam vapor deposition, and then an Au film having a thickness of 500 mm is formed by resistance heating vapor deposition.

  Next, the semiconductor substrate 1 and the nanowire-like semiconductor-filler composite 6 are heated, and the filler 5 and the heat-shrinkable material layer 12 are heat-shrinked. 9D, in addition to the heat shrinkage stress of the filler 5, the heat shrinkage stress of the heat shrinkable material layer 12 acts, so that the nanowire-like semiconductor-filler composite 6 However, the part which is separated from the semiconductor substrate 1 is greatly contracted. As a result, the nanowire-like semiconductor-filler composite 6 is easily peeled from the semiconductor substrate 1.

  The operation of thermally shrinking the filler 5 and the heat-shrinkable material layer 12 can be performed, for example, as follows. First, the semiconductor substrate 1 and the nanowire-like semiconductor-filler composite 6 are placed on a carbon susceptor provided in an infrared heating furnace. Next, after evacuating the inside of the infrared heating furnace, the temperature is raised from room temperature to 400 ° C. over 2 minutes, maintained at a temperature of 400 ° C. for 1 minute, and then cooled to room temperature. By doing so, the heat-shrinkable material layer 12 made of a Ti / Au metal multilayer film can be alloyed at the Ti / Au interface, and the volume can be shrunk.

  Next, as shown in FIG. 9 (e), the support substrate 8 is formed on the heat-shrinkable material layer 12 formed on the surface opposite to the peeling surface 6 a of the nanowire-like semiconductor-filler composite 6. . By doing in this way, the nanowire semiconductor array 13 which consists of the nanowire semiconductor-filler composite body 6, the heat-shrinkable material layer 12, and the support substrate 8 can be obtained.

As the support substrate 8, the same material as that in the first embodiment shown in FIG. For example, when the support substrate 8 is made of SiO ₂ , the support substrate 8 can be formed by bonding to the heat-shrinkable material layer 12 using a conductive carbon double-sided adhesive tape.

  Next, with reference to FIG. 10, the manufacturing method of the nanowire device of the 4th Embodiment of this invention is demonstrated.

  As shown in FIG. 10A, in the method of manufacturing a nanowire device according to the fourth embodiment of the present invention, first, a crystal made of the same material as that of the semiconductor substrate 1 is epitaxially grown on the surface of the semiconductor substrate 1 to obtain a plurality of The nanowire semiconductor 2 is formed.

  As the semiconductor substrate 1, for example, a substrate made of the same semiconductor as in the second embodiment shown in FIG. 8A can be used, and the nanowire-like semiconductor 2 is the first semiconductor shown in FIG. It can be formed in the same manner as in the embodiment.

  Next, as shown in FIG. 10B, the gap between the nanowire-like semiconductors 2 is filled with the filler 5, the nanowire-like semiconductor 2 is embedded in the filler 5, and the nanowire-like semiconductor-filler composite 6 is formed. Form. As the filler 5, the same material as that in the second embodiment shown in FIG. 8B can be used.

  Next, as shown in FIG. 10C, a part of the filler 5 on the side opposite to the semiconductor substrate 1 is removed to expose the tip of the nanowire-like semiconductor 2. Part of the filler 5 can be removed, for example, in the same manner as in the first embodiment shown in FIG.

  Next, as shown in FIG. 10D, an electrode 7 connected to the exposed tip of the nanowire-like semiconductor 2 is formed. The electrode 7 can be formed of, for example, ITO. The electrode 7 made of ITO can be formed using, for example, an RF sputtering apparatus equipped with an ITO target.

  Next, as shown in FIG. 10E, a heat-shrinkable material layer 12 is formed on the electrode 7 formed on the surface of the nanowire-like semiconductor-filler composite 6 opposite to the semiconductor substrate 1. . The heat-shrinkable material layer 12 can be formed using the same material as that in the third embodiment shown in FIG. 9C and the same as in the third embodiment.

  Next, the semiconductor substrate 1 and the nanowire-like semiconductor-filler composite 6 are heated, and the filler 5 and the heat-shrinkable material layer 12 are heat-shrinked. 10F, in addition to the heat shrinkage stress of the filler 5, the heat shrinkage stress of the heat shrinkable material layer 12 acts, so that the nanowire-like semiconductor-filler composite 6 However, the part which is separated from the semiconductor substrate 1 is greatly contracted. As a result, the nanowire-like semiconductor-filler composite 6 is easily peeled from the semiconductor substrate 1.

  The operation of thermally contracting the filler 5 and the heat-shrinkable material layer 12 can be performed in the same manner as in the third embodiment shown in FIG.

  Next, as shown in FIG. 10 (g), the support substrate 8 is formed on the heat-shrinkable material layer 12 formed on the surface opposite to the peeling surface 6 a of the nanowire-like semiconductor-filler composite 6. . By doing in this way, the nanowire semiconductor array 14 which consists of the nanowire semiconductor-filler composite body 6, the electrode 7, the heat-shrinkable material layer 12, and the support substrate 8 can be obtained.

As the support substrate 8, the same material as that in the first embodiment shown in FIG. For example, when the support substrate 8 is made of SiO ₂ , the support substrate 8 can be formed by bonding to the heat-shrinkable material layer 12 using a conductive carbon double-sided adhesive tape.

  In the manufacturing method according to the fourth embodiment shown in FIG. 10, when the electrode 7 is made of a heat-shrinkable material such as ITO, the step shown in FIG. 10 (e) may be omitted. In this case, the electrode 7 made of a heat-shrinkable material exhibits the same action as the heat-shrinkable material layer 12, and the nanowire-like semiconductor-filler composite 6 is easily peeled from the semiconductor substrate 1. Then, as shown in FIG. 10 (h), a nanowire-like semiconductor array 15 composed of the nanowire-like semiconductor-filler composite body 6, the electrode 7, and the support substrate 8 can be obtained.

  Any of the nanowire-like semiconductor arrays 9, 10, 11, 13, 14, and 15 obtained by the manufacturing methods of the above embodiments can be used as a nanowire device for solar cells, light emitting devices, transistors, various sensors, and the like. .

  In the manufacturing method of each of the above embodiments, the nanowire-like semiconductor 2 is formed by epitaxially growing a crystal made of the same material as the semiconductor substrate 1 on the surface of the semiconductor substrate 1. The nanowire-like semiconductor 2 is a semiconductor substrate. 1 may be different. In this case, the semiconductor substrate 1 and the nanowire-like semiconductor 2 are heterojunctioned, and a strain is formed between them, so that the nanowire-like semiconductor-filler composite 6 is peeled from the semiconductor substrate 1. Can be performed more easily.

Of the crystals made of a material different from that of the semiconductor substrate 1, the following can be used as the lattice-matching hetero bond. First, when the semiconductor substrate 1 is GaAs, Al _x Ga _1-X As (0 <x ≦ 1), Ga _x In _1-x As _y P _1-y (x≈ (1 + y) /2.08 In _0.49 Ga _0.51 P, Ge, or the like can be used. When the semiconductor substrate 1 is GaP, Al _x Ga _1- XP (0 <x ≦ 1) or the like can be used. When the semiconductor substrate 1 is InP, Ga _x In _{1- x} As _y P _1-y (x≈0.1894y / (0.4184-0.013y), Ga _0.47 In _0.53 As, etc. can be used. Also, when the semiconductor substrate 1 is ZnSe For example, Ga _x In _1-x As _y P _1-y (x≈ (1.06 + y) /2.06) can be used. When the semiconductor substrate 1 is GaSb, Ga _x In _{1 -x As y Sb 1-y (} y = (0.3835-0.3835x) /0.4210+0.216x) or the like can be used.

  Furthermore, the lattice-matched heterojunction may be formed using a mixed crystal material such as GaInNAs, GaInNP, AlInNP, GANASSb, GaNP, and GaNPAs.

  In addition, among the crystals made of a material different from that of the semiconductor substrate 1, all of the crystals other than those forming the lattice matching heterojunction can be used as those that form the lattice mismatching heterojunction. For example, when the semiconductor substrate 1 is GaAs, InP, InAs, GaP, InGaP (In ≠ 0.49), InGaAs, or the like can be used. When the semiconductor substrate 1 is InP, InAs, GaP, InGaAs (In ≠ 0.49), InGaP, or the like can be used. Further, when the semiconductor substrate 1 is GaP, InAs or the like can be used. When the semiconductor substrate 1 is Si, GaAs, InAs, InP, GaP, Ge, InGaAs, InGaP, or the like can be used. Further, when the semiconductor substrate 1 is Ge, InAs, InP, GaP, or the like can be used.

  In the manufacturing method of each embodiment, the diameter of the circular hole 3 of the amorphous film 4 covering a part of the surface of the semiconductor substrate 1 may be smaller than the diameter of the nanowire-shaped semiconductor 2. In this case, since a strain derived from the difference in diameter is formed between the semiconductor substrate 1 and the nanowire-like semiconductor 2, an operation of peeling the nanowire-like semiconductor-filler composite 6 from the semiconductor substrate 1 is further performed. It can be done easily.

  Further, in the manufacturing method of each of the embodiments, the amorphous film 4 covering a part of the surface of the semiconductor substrate 1 is formed, and the crystal is formed on the surface of the semiconductor substrate 1 exposed in the circular hole 3 of the amorphous film 4. Is grown epitaxially to form the nanowire-like semiconductor 2. However, instead of forming the amorphous film 4 on the surface of the semiconductor substrate 1, a catalyst metal may be disposed, and the crystal may be epitaxially grown through the catalyst metal.

  In the manufacturing method of each of the above embodiments, the semiconductor substrate 1 is reused a plurality of times by forming the nanowire semiconductor 2 on the surface of the semiconductor substrate 1 from which the nanowire semiconductor-filler composite 6 has been peeled off. Can do. The semiconductor substrate 1 is reused when the semiconductor substrate 1 itself is an expensive one made of a compound semiconductor such as GaAs, InP, InAs or the like, or the surface of the semiconductor substrate 1 is coated with an amorphous film 4 and amorphous. This is particularly advantageous when complicated processing such as forming the circular holes 4 in the material film 4 by lithography is required.

  DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate, 2 ... Nanowire-like semiconductor, 4 ... Amorphous film, 5 ... Filler, 6 ... Nanowire-like semiconductor-filler composite, 7 ... Electrode, 8 ... Support substrate, 9, 10, 11, 13 , 14, 15 ... nanowire semiconductor array, 12 ... heat shrinkable material layer.

Claims (12)

Forming a plurality of nanowire semiconductors by epitaxially growing a crystal on a surface of a semiconductor substrate;
Filling the gap between the nanowire-like semiconductor with a filler to embed the nanowire-like semiconductor to form a nanowire-like semiconductor-filler composite;
Forming a support substrate on a surface of the nanowire-like semiconductor-filler composite opposite to the semiconductor substrate;
Separating the nanowire-like semiconductor-filler composite from the semiconductor substrate by external force to form a nanowire-like semiconductor array comprising the nanowire-like semiconductor-filler composite and the support substrate. A method for manufacturing a nanowire device. In the manufacturing method of the nanowire device according to claim 1,
After filling the gap between the nanowire-like semiconductors with the filler to embed the nanowire-like semiconductor to form a nanowire-like semiconductor-filler composite, a part of the filler on the side opposite to the semiconductor substrate is removed. Exposing the tip of the nanowire-like semiconductor;
Forming an electrode connected to the exposed tip of the nanowire-like semiconductor;
Forming the support substrate on the electrode. A method for producing a nanowire device, comprising: Forming a plurality of nanowire semiconductors by epitaxially growing a crystal on a surface of a semiconductor substrate;
Filling the gap between the nanowire-like semiconductor with a filler to embed the nanowire-like semiconductor to form a nanowire-like semiconductor-filler composite;
The nanowire-like semiconductor array comprising the nanowire-like semiconductor-filler composite by thermally shrinking the filler and peeling the nanowire-like semiconductor-filler composite from the semiconductor substrate by the heat shrinkage stress of the filler. And a step of forming a nanowire device. In the manufacturing method of the nanowire device according to claim 3,
The nanowire-like semiconductor is filled with a filler to bury the nanowire-like semiconductor to form a nanowire-like semiconductor-filler composite, and then the nanowire-like semiconductor-filler composite is opposite to the semiconductor substrate. And a step of forming a heat-shrinkable material layer on the surface of the nanowire device. 4. The method of manufacturing a nanowire device according to claim 3, wherein after filling the gap between the nanowire-like semiconductors with a filler to bury the nanowire-like semiconductor to form a nanowire-like semiconductor-filler composite, Removing a portion of the filler on the opposite side to expose the tip of the nanowire-like semiconductor;
Forming an electrode connected to the exposed tip of the nanowire-like semiconductor, and forming a nanowire-like semiconductor-filler composite including the electrode.   6. The method of manufacturing a nanowire device according to claim 5, further comprising a step of forming a heat-shrinkable material layer on the electrode.   The method of manufacturing a nanowire device according to any one of claims 3 to 6, further comprising a step of forming a support substrate on an outermost layer of the nanowire-like semiconductor array.   8. The method of manufacturing a nanowire device according to claim 1, wherein a plurality of nanowire-like semiconductors are formed by epitaxially growing a crystal made of a material different from the semiconductor substrate on the surface of the semiconductor substrate. A method for producing a nanowire device, comprising:   9. The method of manufacturing a nanowire device according to claim 1, wherein a part of the surface of the semiconductor substrate is covered with an amorphous film and exposed from the amorphous film. A method of manufacturing a nanowire device, comprising: forming a plurality of nanowire-like semiconductors by epitaxially growing a crystal on the surface of the substrate.   10. The method of manufacturing a nanowire device according to claim 9, wherein the diameter of the surface of the semiconductor substrate exposed from the amorphous film is smaller than the diameter of the nanowire-like semiconductor. Method.   9. The method of manufacturing a nanowire device according to claim 1, wherein a catalyst metal is disposed on a surface of the semiconductor substrate, and a crystal is epitaxially grown through the catalyst metal to form a plurality of nanowire-like semiconductors. The manufacturing method of the nanowire device characterized by including the process to form.   12. The method of manufacturing a nanowire device according to claim 1, wherein a plurality of nanowire-like semiconductors are formed by epitaxially growing a crystal on a surface of the semiconductor substrate from which the nanowire-like semiconductor-filler composite is separated. A method of manufacturing a nanowire device, comprising: forming a nanowire device.