Production of semiconductor nanowires directly from solid particles
10978298 ยท 2021-04-13
Assignee
Inventors
Cpc classification
H01M4/136
ELECTRICITY
Y02E60/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M4/1397
ELECTRICITY
H01M2004/021
ELECTRICITY
International classification
H01L21/02
ELECTRICITY
H01M4/1397
ELECTRICITY
H01M4/58
ELECTRICITY
H01M4/136
ELECTRICITY
Abstract
Disclosed is a process for producing semiconductor nanowires having a diameter or thickness from 2 nm to 100 nm, the process comprising: (A) preparing a semiconductor material particulate having a size from 50 nm to 500 m, selected from Ga, In, Ge, Sn, Pb, P, As, Sb, Bi, Te, a combination thereof, a compound thereof, or a combination thereof with Si; (B) depositing a catalytic metal, in the form of nanoparticles having a size from 1 nm to 100 nm or a coating having a thickness from 1 nm to 100 nm, onto surfaces of the semiconductor material particulate to form a catalyst metal-coated semiconductor material; and (C) exposing the catalyst metal-coated semiconductor material to a high temperature environment, from 100 C. to 2,500 C., for a period of time sufficient to enable a catalytic metal-assisted growth of multiple semiconductor nanowires from the particulate.
Claims
1. A process for producing semiconductor nanowires having a diameter or thickness from 2 nm to 100 nm, said process comprising: (A) preparing a solid semiconductor material in a particulate solid form having a size from 50 nm to 500 m, wherein said semiconductor material is selected from Ga, In, Sn, Pb, P, As, Sb, Bi, Te, a combination thereof, a compound thereof excluding III-V semiconductor compounds, or a combination thereof with Si having less than 30% by weight of Si; (B) depositing a catalytic metal, in the form of nanoparticles having a size from 1 nm to 100 nm or a coating having a thickness from 1 nm to 100 nm, onto surfaces of said solid semiconductor material particulate to form a catalyst metal-coated semiconductor material; and (C) exposing said catalyst metal-coated semiconductor material to a high temperature environment, from 100 C. to 2,500 C., for a period of time sufficient to enable a catalytic metal-assisted growth of multiple semiconductor nanowires from said semiconductor material particulate.
2. The process of claim 1, wherein said solid semiconductor material particulate has a diameter from 100 nm to 10 m.
3. A process for producing semiconductor nanowires having a diameter or thickness from 2 nm to 100 nm, said process comprising: (A) preparing a solid semiconductor material in a particulate solid form having a size from 50 nm to 500 m, wherein said semiconductor material is selected from Ga, In, Ge, Sn, Pb, P, As, Sb, Bi, Te, a combination thereof, a compound thereof, or a combination thereof with Si having less than 30% by weight of Si; (B) depositing a catalytic metal, in the form of nanoparticles having a size from 1 nm to 100 nm or a coating having a thickness from 1 nm to 100 nm, onto surfaces of said solid semiconductor material particulate to form a catalyst metal-coated semiconductor material, wherein said catalytic metal is selected from Pb, Bi, Sb, Zn, Cd, Ga, In, Zr, Te, P, Sn, or a combination thereof, wherein said catalytic metal is different than said semiconductor material; and (C) exposing said catalyst metal-coated semiconductor material to a high temperature environment, from 100 C. to 2,500 C., for a period of time sufficient to enable a catalytic metal-assisted growth of multiple semiconductor nanowires from said semiconductor material particulate.
4. The process of claim 1, wherein said step of depositing a catalytic metal includes (a) dissolving or dispersing a catalytic metal precursor in a liquid to form a precursor solution, (b) bringing said precursor solution in contact with surfaces of said solid semiconductor particulate material, (c) removing said liquid; and (d) chemically or thermally converting said catalytic metal precursor to said catalytic metal coating or nanoparticles.
5. The process of claim 4, wherein said step (d) of chemically or thermally converting said catalytic metal precursor is conducted concurrently with the procedure (C) of exposing said catalyst metal-coated mixture mass to a high temperature environment.
6. The process of claim 4, wherein said catalytic metal precursor is a salt or organo-metal molecule of a metal selected from Cu, Ni, Co, Mn, Fe, Ti, Al, Ag, Au, Pt, Pd, Pb, Bi, Sb, Zn, Cd, Ga, In, Zr, Te, P, Sn, or a combination thereof.
7. The process of claim 4, wherein said catalytic metal precursor is selected from a nitrate, acetate, sulfate, phosphate, hydroxide, or carboxylate of a metal selected from Cu, Ni, Co, Mn, Fe, Ti, Al, Ag, Au, Pt, Pd, Pb, Bi, Sb, Zn, Cd, Ga, In, Zr, Te, P, Sn, or a combination thereof.
8. The process of claim 4, wherein said catalytic metal precursor is selected from a nitrate, acetate, sulfate, phosphate, hydroxide, or carboxylate of a transition metal.
9. The process of claim 4, wherein said catalytic metal precursor is selected from copper nitrate, nickel nitrate, cobalt nitrate, manganese nitrate, iron nitrate, titanium nitrate, aluminum nitrate, copper acetate, nickel acetate, cobalt acetate, manganese acetate, iron acetate, titanium acetate, aluminum acetate, copper sulfate, nickel sulfate, cobalt sulfate, manganese sulfate, iron sulfate, titanium sulfate, aluminum sulfate, copper phosphate, nickel phosphate, cobalt phosphate, manganese phosphate, iron phosphate, titanium phosphate, aluminum phosphate, copper hydroxide, nickel hydroxide, cobalt hydroxide, manganese hydroxide, iron hydroxide, titanium hydroxide, aluminum hydroxide, copper carboxylate, nickel carboxylate, cobalt carboxylate, manganese carboxylate, iron carboxylate, titanium carboxylate, aluminum carboxylate, or a combination thereof.
10. The process of claim 1, wherein said step of depositing a catalytic metal is conducted by a procedure of physical vapor deposition, chemical vapor deposition, sputtering, plasma deposition, laser ablation, plasma spraying, ultrasonic spraying, printing, electrochemical deposition, electrode plating, electrodeless plating, chemical plating, or a combination thereof.
11. The process of claim 1, wherein said procedure of exposing said catalyst metal-coated semiconductor material to a high temperature environment is conducted in a protective atmosphere of an inert gas, nitrogen gas, hydrogen gas, a mixture thereof, or in a vacuum.
12. The process of claim 1, wherein said semiconductor material and said catalytic metal form an eutectic point and said procedure of exposing said catalyst metal-coated semiconductor material to a high temperature environment includes exposing said material to a temperature equal to or higher than said eutectic point for a desired period of time and then bringing said material to a temperature below said eutectic point.
13. The process of claim 12, wherein said exposure temperature is higher than said eutectic temperature by 0.5 to 500 degrees in Celsius scale.
14. The process of claim 1, further comprising a procedure of removing said catalytic metal from said semiconductor nanowires.
15. The process of claim 1, further comprising a procedure of mixing semiconductor nanowires with a carbonaceous or graphitic material as a conductive additive and an optional binder material to form an electrode layer, wherein said carbonaceous or graphitic material is selected from a chemical vapor deposition carbon, physical vapor deposition carbon, amorphous carbon, chemical vapor infiltration carbon, polymeric carbon or carbonized resin, pitch-derived carbon, natural graphite, artificial graphite, mesophase carbon, mesophase pitch, mesocarbon microbead, soft carbon, hard carbon, coke, carbon fiber, carbon nano-fiber, carbon nano-tube, carbon black, or a combination thereof.
16. A battery electrode containing semiconductor nanowires produced by the process of claim 1.
17. A lithium battery containing semiconductor nanowires produced by the process of claim 1 as an anode active material.
18. A process for producing semiconductor nanowires having a diameter or thickness from 2 nm to 100 nm, said process comprising: a) preparing a solid semiconductor material in a particulate solid form having a size from 50 nm to 100 m, wherein said semiconductor material is selected from Ga, In, Sn, Pb, P, As, Sb, Bi, Te, a combination thereof, a compound thereof excluding III-V semiconductor compounds, or a combination thereof with Si having no greater than 30% by weight of Si; b) depositing a catalyst metal precursor onto surfaces of said solid semiconductor material particulate to form a catalyst metal precursor-coated semiconductor material; and c) exposing said catalyst metal precursor-coated semiconductor material to a high temperature environment, from 100 C. to 2,500 C., for a period of time sufficient to convert said catalyst metal precursor to a metal catalyst in the form of nanoparticles having a size from 1 nm to 100 nm or a coating having a thickness from 1 nm to 100 nm in physical contact with said semiconductor material particulate, and enable a catalyst metal-assisted growth of multiple semiconductor nanowires from said semiconductor material particulate.
19. The process of claim 18, wherein said semiconductor material and said catalyst metal form an eutectic point and said step (c) of exposing said catalyst metal precursor-coated semiconductor material to said high temperature environment includes exposing said material to an exposure temperature equal to or higher than said eutectic point for a desired period of time and then bringing said material to a temperature below said exposure temperature for a desired period of time or at a desired temperature decreasing rate.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
(8) The present invention provides a process for initiating and growing semiconductor nanowires from micron or sub-micron scaled semiconductor particles having an original particle diameter (prior to nanowire growth) from 50 nm to 500 m (preferably from 100 nm to 20 m). In other words, the starting material is micron or sub-micron scaled semiconductor particles, which are thermally and catalytically converted directly into nano-scaled, wire-shaped structures having a diameter or thickness from 2 nm to 100 nm.
(9) Studies using scanning electron microscopy (SEM) indicate that tens of nanowires can be grown or extruded out from a starting solid semiconductor particle. As an example,
(10) There are several advantages associated with this process. For instance, there is no chemical reaction (such as converting SiH.sub.4 into Si in a CVD process) and the process does not involve any undesirable chemical, such as silane, which is toxic. There is no danger of explosion, unlike the process of converting GeO.sub.2 to Ge or SiO.sub.2 to Si using magnesium vapor. Other additional advantages will become more transparent later.
(11) As illustrated in
(12) The starting semiconductor particles preferably have a diameter from 100 nm to 10 m, more preferably <3 m. The starting semiconductor particles are preferably spherical, cylindrical, or platelet (disc, ribbon, etc.) in shape, but can be of any shape. Semiconductor particles of various shapes and various particle sizes are commercially available.
(13) It may be noted that this high temperature range depends on the catalytic metal used. Two examples are used herein to illustrate the best mode of practice. Shown in
(14) In the SnBi binary system, there exists a eutectic point at a eutectic temperature Te=139 C. and eutectic composition Ce=46% (atomic percentage of Bi). A mass of Bi-coated Sn particles may be slowly heated to above Te (e.g. a high temperature from 139.5 C. to 230 C., lower than both the melting temperature of the semiconductor, 231.9 C., and the melting temperature of the catalyst metal, 271 C.). The heating rate can be from 1 to 100 degrees/min (centigrade scale). One can allow the Bi-coated Sn particles to stay at this high temperature (say 170 C.) for 1 minute to 3 hours and then cool the material down to 145 C. (slightly above Te) and/or even 135 C. (slightly below Te) for 1-180 minutes. This will lead to the formation of Sn nanowires from the coated Sn particles.
(15) In the GeAl binary system, there exists a eutectic point at a eutectic temperature Te=420 C. and eutectic composition Ce=71.6% (atomic percentage of Al). A mass of Al-coated Ge particles may be slowly heated to above Te (e.g. a high temperature from 421 C. to 600 C., lower than both the melting temperature of the semiconductor, 938.2 C., and the melting temperature of the catalyst metal, 660.3 C.). The heating rate can be from 1 to 100 degrees/min (centigrade scale). One can allow the Al-coated Ge particles to stay at this high temperature (say 460 C.) for 1 minute to 3 hours and then cool the material down to 430 C. (slightly above Te) and/or even 415 C. (slightly below Te) for 1-180 minutes. This will lead to the formation of Ge nanowires from the coated Sn particles. Alternatively, one may choose to cool the material slowly down from 460 C. (after staying at this temperature for a desired period of time) to room temperature.
(16) In some embodiments, the step of depositing a catalytic metal includes: (a) dissolving or dispersing a catalytic metal precursor in a liquid to form a precursor solution; e.g. dissolving nickel nitrate, Ni(NO.sub.3).sub.2, in water; (b) bringing the precursor solution in contact with surfaces of semiconductor particles; e.g. immersing the particles into the Ni(NO.sub.3).sub.2-water solution; (c) removing the liquid component; e.g. vaporizing water of the Ni(NO.sub.3).sub.2-water solution, allowing Ni(NO.sub.3).sub.2 to coat on the surfaces of the semiconductor particles; and (d) chemically or thermally converting the catalytic metal precursor (e.g. Ni(NO.sub.3).sub.2) to the catalytic metal coating or metal nanoparticles; e.g. by heating the Ni(NO.sub.3).sub.2-coated mass at 450-650 C. in a reducing environment (e.g. in a flowing gas mixture of hydrogen and argon).
(17) In one embodiment, the step (d) of chemically or thermally converting the catalytic metal precursor is conducted concurrently with the step of exposing the catalyst metal-coated semiconductor particles to a high temperature environment.
(18) In certain embodiments, the catalytic metal precursor is a salt or organo-metal molecule of a metal selected from Cu, Ni, Co, Mn, Fe, Ti, Al, Ag, Au, Pt, Pd, Pb, Bi, Sb, Zn, Cd, Ga, In, Zr, Te, P, Sn, or a combination thereof.
(19) In some preferred embodiments, the catalytic metal precursor is selected from a nitrate, acetate, sulfate, phosphate, hydroxide, or carboxylate of a metal selected from Cu, Ni, Co, Mn, Fe, Ti, Al, Ag, Au, Pt, Pd, Pb, Bi, Sb, Zn, Cd, Ga, In, Zr, Te, P, Sn, or a combination thereof.
(20) In some embodiments, the catalytic metal precursor is selected from a nitrate, acetate, sulfate, phosphate, hydroxide, or carboxylate of a transition metal. In certain embodiments, for instance, the catalytic metal precursor is selected from copper nitrate, nickel nitrate, cobalt nitrate, manganese nitrate, iron nitrate, titanium nitrate, aluminum nitrate, copper acetate, nickel acetate, cobalt acetate, manganese acetate, iron acetate, titanium acetate, aluminum acetate, copper sulfate, nickel sulfate, cobalt sulfate, manganese sulfate, iron sulfate, titanium sulfate, aluminum sulfate, copper phosphate, nickel phosphate, cobalt phosphate, manganese phosphate, iron phosphate, titanium phosphate, aluminum phosphate, copper carboxylate, nickel carboxylate, cobalt carboxylate, manganese carboxylate, iron carboxylate, titanium carboxylate, aluminum carboxylate, or a combination thereof. Different types of precursor require different temperatures and/or chemical reactants for conversion to the catalytic metal phase. Different catalytic metals enable semiconductor nanowire growth at different temperatures.
(21) The step of depositing a catalytic metal may also be conducted by a procedure of physical vapor deposition (PVD), chemical vapor deposition (CVD), sputtering, plasma deposition, laser ablation, plasma spraying, ultrasonic spraying, printing, electrochemical deposition, electrode plating, electrodeless plating, chemical plating, or a combination thereof.
(22) The procedure of exposing the catalyst metal-coated semiconductor mass to a high temperature environment is preferably conducted in a protective or reducing atmosphere of an inert gas, nitrogen gas, hydrogen gas, a mixture thereof, or in a vacuum.
(23) In one embodiment, the process may further comprise a procedure of removing the residual catalytic metal from the semiconductor nanowires; for instance, via chemical etching or electrochemical etching.
(24) In a desired embodiment, the process of producing semiconductor nanowires is followed by a procedure of incorporating a carbonaceous or graphitic material into the mass of multiple semiconductor nanowires as a conductive additive in the preparation of an anode electrode. This carbonaceous or graphitic material may be selected from a chemical vapor deposition carbon, physical vapor deposition carbon, amorphous carbon, chemical vapor infiltration carbon, polymeric carbon or carbonized resin, pitch-derived carbon, natural graphite, artificial graphite, mesophase carbon, mesophase pitch, mesocarbon microbead, soft carbon, hard carbon, coke, carbon fiber, carbon nano-fiber, carbon nano-tube, carbon black, or a combination thereof.
(25) For instance, multiple Ge nanowires may be readily packed into a porous membrane or mat (with or without a small amount of resin binder), which may be impregnated or infiltrated with carbon under a chemical vapor deposition (CVD) or chemical vapor infiltration condition. This may be accomplished by introducing methane or ethylene gas into the system at a temperature of 500-1,500 C. Alternatively, one may impregnate the porous Ge nanowire membrane with a resin or pitch, which is then heated to carbonize the resin or pitch at a temperature of 350-1,500 C. Alternatively, one may simply blend semiconductor nanowires with particles of a carbon or graphite material with an optional binder resin to form a multi-component mixture.
(26) The following examples are provided for the purpose of illustrating the best mode of practicing the present invention and should not be construed as limiting the scope of the instant invention. The selection of the following semiconductor materials as examples is based on the consideration that they have a high specific capacity when used as an anode active material: Li.sub.4.4Ge (1,623 mAh/g), Li.sub.4.4Sn (993 mAh/g), and Li.sub.3Sb (660 mAh/g).
Example 1: Zinc-Assisted Growth of Sn Nanowires from Sn Particles
(27) Tin particles were coated with a thin layer of Zn using a simple physical vapor deposition up to a thickness of 1.1-3.5 nm. The SnZn system is known to have a eutectic point at Te=198.5 C. and Ce=85.1% Sn. A powder mass of Zn-coated Sn particles (3.5 m in diameter) were heated to 220 C. and allowed to stay at 220 C. for 1 hour and then cooled down to 200 C. and maintained at 200 C. for 30 minutes. The material system was then naturally cooled to room temperature after switching off the power to the oven. The Sn nanowires grown from Sn particles were found to have diameters in the approximate range of 25-65 nm.
Example 2: Gold-Assisted Growth of Ge Nanowires from Ge Particles
(28) Ge particles (platelets of 1.2 m long and 0.25 m thick) were coated with a thin layer of Au using sputtering deposition up to a thickness of 1.5-5.6 nm. The GeAu system is known to have a eutectic point at Te=361 C. and Ce=28% Ge. A powder mass of Au-coated Ge particles were heated to 600 C. and allowed to stay at 600 C. for 2 hours and then cooled down to 370 C. and maintained at 370 C. for 1 hour. The material system was then cooled to 355 C. for 2 hours and then naturally cooled to room temperature after switching off the power to the oven.
(29) Gold catalyst-assisted growth of Ge nanowires from Ge particles occurred during the subsequent cooling process. The diameter of Ge nanowires produced is in the range from 42 nm to 67 nm.
Example 3: Nickel-Assisted Growth of Ge Nanowires from Ge Particles
(30) Ge particles were immersed in a solution of nickel nitrate or nickel acetate in water. Water was subsequently removed and the dried particles were coated with a thin layer of nickel nitrate or nickel acetate. These metal precursor-coated Ge particles were then exposed to a heat treatment in a reducing atmosphere of H.sub.2 and Ar gas according to a desired temperature profile. This profile typically included from room temperature to a reduction temperature of approximately 300-700 C. (for reduction of nickel nitrate or acetate to Ni nanocoating, for instance). The temperature was continued to rise to a final temperature of 762-900 C. for 1-3 hours and the system was allowed to cool down naturally. Nickel metal catalyst-assisted growth of Ge nanowires from Ge particles was found to occur. The diameter of Ge nanowires produced was in the range from 47 nm to 77 nm.
Example 4: Copper-Assisted Growth of Sb Nanowires from Sb Particles
(31) The work began with the preparation of antimony (Sb) particles, which entailed mixing Sb.sub.2O.sub.3 particles with small activated carbon (AC) particles using ball milling. By heating the resulting mixture in a sealed autoclave and heating the mixture to 950 C., antimony was obtained from the oxide by a carhothermal reduction: 2Sb.sub.2O.sub.3+3C.fwdarw.4Sb+3CO.sub.2. The Sb particles produced typically resided in pores of AC, which could be recovered by breaking up the AC particles with ball-milling.
(32) The Sb particles were immersed in a solution of copper acetate in water. Water was subsequently removed and the dried particles were coated with a thin layer of copper acetate. These metal precursor-coated Sb particles were then exposed to a heat treatment in a reducing atmosphere of H.sub.2 and Ar gas according to a desired temperature profile. This profile typically included from room temperature to a reduction temperature of approximately 300-600 C. (for reduction of copper acetate to Cu nanocoating). The temperature was continued to rise to a final temperature of 526-620 C. for 1-3 hours. The system was allowed to cool down to 520 C. for 1 hour and then cooled down naturally to room temperature, resulting in copper metal catalyst-assisted growth of Sb nanowires from Sb particles.
Example 5: Lithium-Ion Batteries Featuring Ge and Sn Nanowires as an Anode Active Material
(33) For electrochemical testing, several types of anodes and cathodes were prepared. For instance, a layer-type of anode was prepared by simply coating slurry of Ge or Sn nanowires, conductive additives, and a binder resin to form an anode layer against a sheet of Cu foil (as an anode current collector).
(34) For instance, the working electrodes were prepared by mixing 75 wt. % active material (Ge or Sn nanowires), 17 wt. % acetylene black (Super-P, as a conductive additive), and 8 wt. % polyvinylidene fluoride (PVDF) as a binder dissolved in N-methyl-2-pyrrolidinoe (NMP). After coating the slurries on Cu foil, the electrodes were dried at 120 C. in vacuum for 2 h to remove the solvent before a compression treatment.
(35) Then, the electrodes were cut into a disk (=12 mm) and dried at 100 C. for 24 h in vacuum. Electrochemical measurements were carried out using CR2032 (3V) coin-type cells with lithium metal as the counter/reference electrode, Celgard 2400 membrane as separator, and 1 M LiPF.sub.6 electrolyte solution dissolved in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) (EC-DEC, 1:1 v/v). Various anode material compositions were evaluated. The cell assembly was performed in an argon-filled glove-box. The CV measurements were carried out using a CH-6 electrochemical workstation at a scanning rate of 1 mV/s. The electrochemical performance of Si nanowires was also evaluated by galvanostatic charge/discharge cycling at a current density of 50-1,000 mA/g, using a LAND electrochemical workstation. Full-cell pouch configurations using lithium iron phosphate and lithium cobalt oxide cathodes were also prepared and tested.
(36) It may be noted that the lithium-ion battery industry has adopted a nomenclature system for a charge or discharge rate. For instance, 1 C charging means completing charging procedure in 1 hour and 2 C charging means completing charging procedure in hours (30 minute). A 10 C charging rate means charging completion in 1/10 hours (6 minutes).
(37) Some experimental results are summarized in
(38) Similar tends were observed for lithium-ion batteries that contain other types of semiconductor nanowires herein produced as the primary anode active material. These observations have demonstrated that smaller-diameter nanowires are significantly more high-rate capable in a lithium-ion battery. The present invention provides a cost-effective process for producing a wide variety of semiconductor nanowires.