DETAILED ACTION
Notice of AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Specification
The Amendments to the Specification with respect to Abstract (on a separate sheet) filed on 10/22/205 has been considered and entered. Therefore the objection of the previous Office Action filed on 06/04/2025 is currently withdrawn.
Response to Amendment
The amendment with respect to claims 1, 4-5, 10, 16 and 19 filed on 10/22/2025 have been fully considered for examination based on their merits. The previously presented claims 2-3, 6-9, 11-15, 17-18, and 20 have been considered.
Response to Arguments
Applicant’s arguments with respect to claim(s) 1-20 have been considered but are moot because the new ground of rejection does not rely on any reference applied in the prior rejection of record for any teaching or matter specifically challenged in the argument.
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
Claim(s) 1, and 4-9 is/are rejected under 35 U.S.C. 103 as being unpatentable over Virginia Robbins, (hereinafter ROBBINS), US 20080038521 A1 in view of Lars Samuelson et al, (hereinafter SAMUELSON), US 20100252808 A1.
Regarding Claim 1, ROBBINS teaches a method of growing nanowires (NWs) (Figs. 24/25, method for preparing nanowires, [0060]), comprising:
forming catalyst particles (Fig. 24, 2406/2412, nucleating particles, suitable metal catalysts/liquid alloy droplet [0024]) comprising a gold-indium alloy (Fig. 24, 2412, liquid alloy droplet, colloids comprising Au, or In, [0024]) on portions of a semiconductor substrate (Fig. 24, 2402, substrate materials) that are exposed by openings (Fig. 24, 2410, voids includes openings, [0220]) of a template layer (Fig. 24, 2404, catalyst-repelling material, [0218]) disposed on the substrate (Fig. 24, 2402, substrate materials);
growing nanowire (Fig. 24, 2408, nanowires) aluminum phosphide (AlP) stubs (AlP nanowires, [0071]) in the openings (Fig. 24, 2410, voids includes openings, [0220]) of the template layer (Fig. 24, 2404, catalyst-repelling material, [0218]) and between the substrate (Fig. 24, 2402, substrate materials) and the catalyst particles (Fig. 24, 2406/2412, nucleating particles, suitable metal catalysts/liquid alloy droplet [0024]); and
growing nanowires (NWs) (Figs. 10, method of growing desired portion of a nanowire), comprising a compound semiconductor material (Figs. 10/11, 1120, desired portion of the nanowire) between the AlP stubs (Figs. 10/11, 1110, sacrificial portion of the nanowire) and the catalyst particles (Figs. 10/11, 1130, stub).
Though ROBBINS teaches a method of growing nanowires comprising a desired portion of the nanowire having different alloy and properties than the sacrificial portion of the nanowires [0167-0171], ROBBINS does not explicitly disclose a method of growing nanowires (NWs), comprising a compound semiconductor material between the AlP stubs and the catalyst particles.
SAMUELSON teaches a method of growing nanowires (NWs) (Figs. 6/9d, a method of producing a nanowires, [0005]), comprising a compound semiconductor material (Fig. 9d, 14, a GaAs nanowire core being a second nanowire segment, [0084]) between the AlP stubs (Fig. 9d, 13, a GaP nucleation layer being a first nanowire segment, [0084]) and the catalyst particles (Fig. 9D, 10, Au seed particle, [0084]). (NOTE: It should be noted that substituting (GaP) for (AlP) is a simple substitution of one known element for another to obtain predictable results [See MPEP2143]).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention (AIA ) to have modified ROBBINS to incorporate the teachings of SAMUELSON such that a method of growing nanowires (NWs), comprising a compound semiconductor material between the AlP stubs and the catalyst particles, so that the control of position and direction of the substrate-grown nanowires are crucial parameters needed for successful fabrication of optical devices as well as most other applications (SAMUELSON, [0084], [0002]).
(Additional Note: Rationale on Combining Art drawings of ROBBINS (Fig. 11) and SAMUELSON (Fig. 9d) for comparison is shown below. The sacrificial portion of NW, the desired portion of NW in ROBBINS are equated to GaP (or AlP) NW and GaAs (or GaP) NW in SAMUELSON).
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Regarding Claim 4, ROBBINS as modified by SAMUELSON teaches the method of claim 1.
SAMUELSON further teaches the method (Figs. 6/9d, a method of producing a nanowires, [0005]), wherein the substrate comprises gallium phosphide (GaP) (Fig. 2b, GaP substrates, [0077], [0083]).
Regarding Claim 5, ROBBINS as modified by SAMUELSON teaches the method of claim 4.
SAMUELSON further teaches the method (Figs. 6/9d, a method of producing a nanowires, [0005]), wherein the NWs comprise GaP NWs (Fig. 1b, [0020], [0033]; i-GaP nanowire, [0082]).
Regarding Claim 6, ROBBINS as modified by SAMUELSON teaches the method of claim 5.
ROBBINS further teaches the method (Figs. 24/25, method for preparing nanowires, [0060]), further comprising:
removing (Fig. 10, method 1000 involves the use of a sacrificial portion of a nanowire to provide more effective removal of the nanowires, [0166]) the GaP NWs (Figs. 10/11, 1120, desired portion of the nanowire) from the substrate (Fig. 11, 1140) by separating (Fig. 10, 1030, protecting desired portion of the nanowire, [0172]) the GaP NWs (Figs. 10/11, 1120, desired portion of the nanowire) from the AlP nanowire stubs (Figs. 10/11, 1110, sacrificial portion of the nanowire); and
removing (Fig. 10, 1040, differentially remove the sacrificial portion of the nanowire, [0173]) the AlP nanowire stubs (Figs. 10/11, 1110, sacrificial portion of the nanowire) from the substrate (Fig. 11, 1140) after separating (Fig. 10, 1030, protecting desired portion of the nanowire, [0172]) the GaP NWs (Figs. 10/11, 1120, desired portion of the nanowire) from the AlP nanowire stubs (Figs. 10/11, 1110, sacrificial portion of the nanowire).
(See also additional note in Claim 1, regarding equating sacrificial portion of the NW and the desired portion of the NW of ROBBINS with actual semiconductor materials of SAMUELSON as annotated in Figure 11 and Figure 9d respectively).
Regarding Claim 7, ROBBINS as modified by SAMUELSON teaches the method of claim 6.
ROBBINS further teaches the method (Figs. 24/25, method for preparing nanowires, [0060]), wherein:
the step of removing (Fig. 10, method 1000 involves the use of a sacrificial portion of a nanowire to provide more effective removal of the nanowires, [0166]) the GaP NWs (Figs. 10/11, 1120, desired portion of the nanowire) from the substrate (Fig. 11, 1140) comprises using sonication (Fig. 10, current removal of nanowires, methods include using ultrasound and mechanical shearing, [0164-0165]) or a polymer matrix (Fig. 8, 806, after processing the nanowires on the growth substrate, the nanowires can be removed from the substrate by coating the nanowires with a polymer to form a composite, and then removing the nanowires from the substrate, [0150], [0154]) to separate the GaP NWs (Figs. 10/11, 1120, desired portion of the nanowire) from the AlP nanowire stubs (Figs. 10/11, 1110, sacrificial portion of the nanowire); and
the step of removing (Fig. 10, 1040, differentially remove the sacrificial portion of the nanowire, [0173]) the AlP nanowire stubs (Figs. 10/11, 1110, sacrificial portion of the nanowire) from the substrate (Fig. 11, 1140) comprises selectively etching the AlP nanowire stubs (Fig. 10, differentially removed by using wet etchant with a etching rate that is significantly higher for the material within the sacrificial than for the material within the desired portion [0173]).
(See also additional note in Claim 1, regarding equating sacrificial portion of the NW and the desired portion of the NW of ROBBINS with actual semiconductor materials of SAMUELSON as annotated in Figure 11 and Figure 9d respectively).
Regarding Claim 8, ROBBINS as modified by SAMUELSON teaches the method of claim 6.
ROBBINS further teaches the method (Figs. 24/25, method for preparing nanowires, [0060]), further comprising reusing the substrate to grow additional GaP NWs stubs after removing the AlP nanowire (Fig. 22, 2200, global transfer process, substrate, (2102) can be used repeatedly for nanowire (2104) growth and transfer after the nanowires that have grown on its surface have been transferred to a transfer substrate (2106), [0207]).
Regarding Claim 9, ROBBINS as modified by SAMUELSON teaches the method of claim 8.
ROBBINS further teaches the method (Figs. 24/25, method for preparing nanowires, [0060]), wherein the step of reusing the substrate comprises repeating (substrate can be used repeatedly for nanowire growth, [0207]) at least 3 times the steps (a recycling process in the production stage can be used, [0092]) of forming the catalyst particles (Fig. 24, 2406/2412, nucleating particles, suitable metal catalysts/liquid alloy droplet [0024]), growing the AlP nanowire stubs (Fig. 24, 2408, AlP nanowires, [0071]), and growing the GaP NWs (Figs. 10/11, 1120, desired portion of the nanowire) between the AlP nanowire stubs (Figs. 10/11, 1110, sacrificial portion of the nanowire) and the catalyst particles (Figs. 10/11, 1130, stub).
(See also additional note in Claim 1, regarding equating sacrificial portion of the NW and the desired portion of the NW of ROBBINS with actual semiconductor materials of SAMUELSON as annotated in Figure 11 and Figure 9d respectively).
Claim(s) 2, and 10 is/are rejected under 35 U.S.C. 103 as being unpatentable over ROBBINS, in view of SAMUELSON, and further in view of Helge Weman et al, (hereinafter WEMAN), US 20150076450 A1.
Regarding Claim 2, ROBBINS as modified by SAMUELSON teaches the method of claim 1.
ROBBINS further teaches the method (Figs. 24/25, method for preparing nanowires, [0060]), wherein the step of forming catalyst particles (Fig. 24, 2406/2412, nucleating particles, suitable metal catalysts/liquid alloy droplet [0024]) comprises: depositing gold particles (Fig. 24, 2406, nucleating particles will be metal catalysts comprise a gold (Au), colloid (i.e. a Au nanoparticle) or Au film, [0024], [0090-0091]) on the exposed portions (Fig. 24, 2410, voids includes openings, [0220]) of the substrate (Fig. 24, 2402, substrate materials).
ROBBINS as modified by SAMUELSON does not teach the method, wherein the step of forming catalyst particles comprises: performing an indium flush to alloy the gold particles with indium to form the catalyst particles which comprise a gold-indium alloy.
WEMAN teaches the method (VLS method, e.g. MBE, or MOVP, growing of semiconductor nanowires involve metal catalysis, [0124]), wherein the step of forming catalyst particles (for catalyst-assisted growth, the catalyst may be Au or Ag, [0096]) comprises: performing an indium flush (a Ga/In flux can be supplied to the substrate surface, [0099]) to alloy the gold particles with indium to form the catalyst particles which comprise a gold-indium alloy (thin Au film tuned into Au particles and alloyed with Ga from the substrate forming Au-Ga liquid particles, [0153]; It is thus possible to use another element from group III as a catalyst for growing a III-V nanowire e.g. use Ga as a catalyst for an In (group V) nanowire and so on [0096]).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention (AIA ) to have ROBBINS as modified by SAMUELSON to incorporate the teachings of WEMAN such that the method, wherein the step of forming catalyst particles comprises: performing an indium flush to alloy the gold particles with indium to form the catalyst particles which comprise a gold-indium alloy, so that the eutectic alloy form the particle-like droplets on the substrate and these droplets form the points where nanowires can grow; as the nanowire grows, the liquid (e.g.) gold droplet stays on the top of the nanowire, and may therefore play a major role in contacting top graphitic layers of the semiconductor structure (WEMAN, [0096]).
Regarding Claim 10, ROBBINS teaches a method of growing nanowires (NWs) (Figs. 24/25, method for preparing nanowires, [0060]), comprising:
depositing gold particles (Fig. 24, 2406/2412, nucleating particles, suitable metal catalysts/liquid alloy droplet, colloids comprising Au, or In, [0024]) on portions of a gallium phosphide (GaP) substrate (Fig. 24, 2402, substrate materials, [0025]; suitably a crystallographic substrate, such as a silicon or other semiconductor material, [0218]; (for e.g. GaP, [0071]);
growing aluminum phosphide (AlP) nanowire stubs (Fig. 24, 2408, AlP nanowires, [0071]) in the openings (Fig. 24, 2410, voids includes openings, [0220]) of the template layer (Fig. 24, 2404, catalyst-repelling material, [0218]) and between the substrate (Fig. 24, 2402, substrate materials, [0025]) and the catalyst particles (Fig. 24, 2406/2412, nucleating particles, suitable metal catalysts/liquid alloy droplet, colloids comprising Au, or In, [0024]); and
growing GaP NWs (Figs. 10/11, 1120, desired portion of the nanowire) between the AlP nanowire stubs (Figs. 10/11, 1110, sacrificial portion of the nanowire) and the catalyst particles (Figs. 10/11, 1130, stub).
Though ROBBINS teaches a method of growing nanowires comprising a desired portion of the nanowire on a Si or other crystallographic semiconductor materials, having different alloy and properties than the sacrificial portion of the nanowires [0167-0171], ROBBINS does not explicitly disclose a method comprising: a gallium phosphide (GaP) substrate; performing an indium flush to alloy the gold particles with indium to form gold- indium alloy catalyst particles; and growing GaP NWs between the AlP stubs and the catalyst particles.
SAMUELSON teaches a method of growing nanowires (NWs) (Figs. 6/9d, a method of producing a nanowires, [0005]), comprising: a gallium phosphide (GaP) substrate (Fig. 2b, GaP substrates, [0077], [0083]); performing an indium flush to alloy the gold particles with indium to form gold- indium alloy catalyst particles; and growing GaP NWs (Fig. 9d, 14, a GaAs nanowire core being a second nanowire segment, [0084]) between the AlP stubs (Fig. 9d, 13, a GaP nucleation layer being a first nanowire segment, [0084]) and the catalyst particles (Fig. 9D, 10, Au seed particle, [0084]). (NOTE: It should be noted that substituting (GaP) for (AlP) is a simple substitution of one known element for another to obtain predictable results [See MPEP2143]).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention (AIA ) to have modified ROBBINS to incorporate the teachings of SAMUELSON such that a method of growing nanowires (NWs), comprising: a gallium phosphide (GaP) substrate; performing an indium flush to alloy the gold particles with indium to form gold- indium alloy catalyst particles; and growing GaP NWs between the AlP stubs and the catalyst particles, so that the control of position and direction of the substrate-grown nanowires are crucial parameters needed for successful fabrication of optical devices as well as most other applications (SAMUELSON, [0084], [0002]).
ROBBINS as modified by SAMUELSON does not teach a method of growing nanowires (NWs), comprising: performing an indium flush to alloy the gold particles with indium to form the catalyst particles which comprise a gold-indium alloy.
WEMAN teaches a method of growing nanowires (NWs), (VLS method, e.g. MBE, or MOVP, growing of semiconductor nanowires involve metal catalysis, [0124]), comprising: performing an indium flush (a Ga/In flux can be supplied to the substrate surface, [0099]) to alloy the gold particles with indium to form the catalyst particles which comprise a gold-indium alloy (thin Au film tuned into Au particles and alloyed with Ga from the substrate forming Au-Ga liquid particles, [0153]; It is thus possible to use another element from group III as a catalyst for growing a III-V nanowire e.g. use Ga as a catalyst for an In (group V) nanowire and so on [0096]).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention (AIA ) to have ROBBINS as modified by SAMUELSON to incorporate the teachings of WEMAN such that a method of growing nanowires (NWs), comprising: performing an indium flush to alloy the gold particles with indium to form the catalyst particles which comprise a gold-indium alloy, so that the eutectic alloy form the particle-like droplets on the substrate and these droplets form the points where nanowires can grow; as the nanowire grows, the liquid (e.g.) gold droplet stays on the top of the nanowire, and may therefore play a major role in contacting top graphitic layers of the semiconductor structure (WEMAN, [0096]).
Claim(s) 3, and 11-13 is/are rejected under 35 U.S.C. 103 as being unpatentable over ROBBINS, in view of SAMUELSON, further in view of WEMAN, and further in view of Werner Seifert et al, (hereinafter SEIFERT), US 20080142926 A1.
Regarding Claim 3, ROBBINS as modified by SAMUELSON and WEMAN teaches the method of claim 2.
Though WEMAN teaches the Gallium/Indium flux used for producing liquid-alloy droplets, like Au-Ga (or Au-In) catalyst particles, ROBBINS as modified by SAMUELSON and WEMAN does not explicitly disclose the method, wherein the step of performing the indium flush comprises providing an indium metalorganic vapor into a reaction chamber containing the substrate, at a temperature between 260 °C and 400 °C, for at least 10 seconds.
SEIFERT further teaches the method (method of growing InP nanowhiskers using low-pressure metal-organic vapor phase epitaxy (MOVPE), [0058]), wherein the step of performing the indium flush comprises providing an indium metalorganic vapor into a reaction chamber containing the substrate, at a temperature between 260 °C and 400 °C, for at least 10 seconds (introducing trimethylindium (TMI) into the reactor cell using MOVPE process over the (001) InP substrates, and the samples were heated up to 420oC over 5 minutes (or typical growth time was 8 minutes) [0058]).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention (AIA ) to have ROBBINS as modified by SAMUELSON and WEMAN to incorporate the teachings of SEIFERT such that the method, wherein the step of performing the indium flush comprises providing an indium metalorganic vapor into a reaction chamber containing the substrate, at a temperature between 260 °C and 400 °C, for at least 10 seconds, so that this method of producing whiskers differs from the often-used procedure of whisker growth, where Au particles are annealed at higher temperature prior to whisker growth in order to de-oxidize the surface and alloy the Au catalyst with the semiconductor material, (SEIFERT, [0058]).
Regarding Claim 11, ROBBINS as modified by SAMUELSON and WEMAN teaches the method of claim 10.
Though WEMAN teaches the Gallium/Indium flux used for producing liquid-alloy droplets, like Au-Ga (or Au-In) catalyst particles, ROBBINS as modified by SAMUELSON and WEMAN does not explicitly disclose the method, wherein the step of performing the indium flush comprises heating the substrate to a temperature ranging from 260 °C to 400 °C, while providing an indium-containing vapor to the substrate.
SEIFERT further teaches the method (method of growing InP nanowhiskers using low-pressure metal-organic vapor phase epitaxy (MOVPE), [0058]), wherein the step of performing the indium flush comprises heating the substrate to a temperature ranging from 260 °C to 400 °C, while providing an indium-containing vapor to the substrate (introducing trimethylindium (TMI) into the reactor cell using MOVPE process over the (001) InP substrates, and the samples were heated up to 420oC [0058]).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention (AIA ) to have ROBBINS as modified by SAMUELSON and WEMAN to incorporate the teachings of SEIFERT such that the method, wherein the step of performing the indium flush comprises heating the substrate to a temperature ranging from 260 °C to 400 °C, while providing an indium-containing vapor to the substrate, so that this method of producing whiskers differs from the often-used procedure of whisker growth, where Au particles are annealed at higher temperature prior to whisker growth in order to de-oxidize the surface and alloy the Au catalyst with the semiconductor material, (SEIFERT, [0058]).
Regarding Claim 12, ROBBINS as modified by SAMUELSON, WEMAN and SEIFERT teaches the method of claim 11.
SEIFERT further teaches the method (method of growing InP nanowhiskers using low-pressure metal-organic vapor phase epitaxy (MOVPE), [0058]), wherein the indium-containing vapor is provided for a time period ranging from 10 seconds to 120 seconds (introducing trimethylindium (TMI) into the reactor cell using MOVPE process over the (001) InP substrates, and the samples were heated up to 420oC over 5 minutes (or typical growth time was 8 minutes) [0058]).
Regarding Claim 13, ROBBINS as modified by SAMUELSON and WEMAN teaches the method of claim 10.
WEMAN teaches a method (VLS method, e.g. MBE, or MOVP, growing of semiconductor nanowires involve metal catalysis, [0124]), further comprising annealing the substrate after the indium flush (a Ga/In flux can be supplied to the substrate surface for a period of time to initiate the formation of Ga/In droplets on the surface upon heating of the substrate, [0099]) is performed and before the AlP stubs are grown (the substrate temperature can then be set to a temperature suitable for the growth of the nanowire, [0099]), the annealing comprising: heating the substrate at a temperature ranging from 625 °C to 675 °C (the growth temperature may be in the range of 300 to 700 oC, [0099]), while flowing a phosphine-containing vapor to the substrate; and then cooling the substrate to a temperature ranging from 415 °C to about 465 °C (for InAs (another similar III-V compound is AlP), the range is lower, for example 420 to 540 oC, e.g. 450 oC, [0099]).
ROBBINS as modified by SAMUELSON and WEMAN does not explicitly disclose the method, further comprising: the annealing comprising: heating the substrate at a temperature ranging from 625 °C to 675 °C, while flowing a phosphine-containing vapor to the substrate.
SEIFERT teaches the method (method of growing nanowhiskers, [0023]), further comprising: the annealing comprising: heating the substrate at a temperature ranging from 625 °C to 675 °C (at high temperature (>500 oC), [0064]), while flowing a phosphine-containing vapor to the substrate (a constant phosphine flow was supplied to the reactor cell [0058]).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention (AIA ) to have ROBBINS as modified by SAMUELSON and WEMAN to incorporate the teachings of SEIFERT such that the method, further comprising: the annealing comprising: heating the substrate at a temperature ranging from 625 °C to 675 °C, while flowing a phosphine-containing vapor to the substrate, so that the InP will be locally dissolved in a reaction with the Au, resulting in the formation of a pit (SEIFERT, Figure 2, [0064]).
Claim(s) 14-15 is/are rejected under 35 U.S.C. 103 as being unpatentable over ROBBINS, in view of SAMUELSON, further in view of WEMAN, further in view of SEIFERT, and further in view of Lars Samuelson et al, (hereinafter SAMUELSON2), US 20060057360 A1.
Regarding Claim 14, ROBBINS as modified by SAMUELSON, WEMAN and SEIFERT teaches the method of claim 13.
ROBBINS teaches the method of (Figs. 24/25, method for preparing nanowires, [0060]), wherein the step of growing the AlP nanowire stubs (Fig. 2, 214, nanowires of desired size and orientation) comprises maintaining the substrate at the temperature ranging from 415 °C to about 465 °C (Fig. 2, 204, temperature 1 to 208, temperature 2), while flowing a phosphine-containing and aluminum-containing vapor to the substrate (Fig. 2, 204/208, contact with precursor gas mixture A/gas mixture B).
SAMUELSON further teaches the method (Figs. 6/9d, a method of producing a nanowires, [0005]), wherein the step of growing the AlP nanowire stubs (Fig. 9d, 14, i-GaP (first segment) nanowire, [0079]) comprises maintaining the substrate at the temperature ranging from 415 °C to about 465 °C, (350 to 650 oC, [0065]) while flowing a phosphine-containing and aluminum-containing vapor to the substrate (the metal organic sources used were TMGa and TMIn together with PH3 gases, [0082]; it should be noted that substituting (Trimethylgallium, TMG, Trimethylindium, TMI) for (Trimethylaluminum, TMAl) is a simple substitution of one known element for another to obtain predictable results [See MPEP2143]).
ROBBINS as modified by SAMUELSON, WEMAN and SEIFERT does not explicitly disclose the method, wherein the step of growing the AlP nanowire stubs comprises maintaining the substrate at the temperature ranging from 415 °C to about 465 °C, while flowing a phosphine-containing and aluminum-containing vapor to the substrate.
SAMUELSON2 further teaches the method ([0036-0037]), wherein the step of growing the AlP nanowire stubs (Fig. 5, 64, AlP as a coaxial shell around each nanowhisker, [0043]) comprises maintaining the substrate at the temperature ranging from 415 °C to about 465 °C (400, 430, 460, 490 and 520o C, [0059]), while flowing a phosphine-containing and aluminum-containing vapor to the substrate ([0059], [0076]; it should be noted that substituting (Trimethylgallium, TMG, Trimethylindium, TMI) for (Trimethylaluminum, TMAl) is a simple substitution of one known element for another to obtain predictable results (See MPEP2143)).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention (AIA ) to have ROBBINS as modified by SAMUELSON, WEMAN and SEIFERT to incorporate the teachings of SAMUELSON2 such that the method, wherein the step of growing the AlP nanowire stubs comprises maintaining the substrate at the temperature ranging from 415 °C to about 465 °C, while flowing a phosphine-containing and aluminum-containing vapor to the substrate, so that the nanowhiskers grow upwards at a constant rate in the <111>B direction, with hexagonal cross section; [001] nanowires have a square cross section (SAMUELSON2, [0059]).
Regarding Claim 15, ROBBINS as modified by SAMUELSON, WEMAN, SEIFERT, and SAMUELSON2 teaches the method of claim 14.
SAMUELSON further teaches the method (Figs. 6/9d, a method of producing a nanowires, [0005]), wherein the phosphine-containing and aluminum- containing vapor comprises phosphine (PH3) and trimethylaluminum (TMAl) (the metal organic sources used were TMGa and TMIn together with PH3 gases, [0082]; it should be noted that substituting (Trimethylgallium, TMG, Trimethylindium, TMI) for (Trimethylaluminum, TMAl) is a simple substitution of one known element for another to obtain predictable results [See MPEP2143]).
SAMUELSON2 further teaches the method ([0036-0037]), wherein the phosphine-containing and aluminum- containing vapor comprises phosphine (PH3) and trimethylaluminum (TMAl) ([0059], [0076]; it should be noted that substituting (Trimethylgallium, TMG, Trimethylindium, TMI) for (Trimethylaluminum, TMAl) is a simple substitution of one known element for another to obtain predictable results (See MPEP2143)).
Claim(s) 16-17, and 19-20 is/are rejected under 35 U.S.C. 103 as being unpatentable over ROBBINS, in view of SAMUELSON, further in view of WEMAN, further in view of SEIFERT, further in view of SAMUELSON2, and further in view of Sung Yi, (hereinafter YI), US 20050266662 A1.
Regarding Claim 16 ROBBINS as modified by SAMUELSON, WEMAN, SEIFERT, and SAMUELSON2 teaches the method of claim 14.
ROBBINS further teaches the method of (Figs. 24/25, method for preparing nanowires, [0060]), wherein the growing GaP NWs comprises (Fig. 2, 214, nanowires of desired size and orientation): stopping the flow of the phosphine and aluminum-containing vapor (Fig. 2, 204, contact with precursor gas mixture A at the first temperature; one or more additional precursor gas mixtures comprising PH3, [0014]) to the substrate; flowing an acid comprising HCl or HBr to the substrate (hydrofluoric (HF) acid, [0157]); and flowing a phosphine and gallium-containing vapor to the substrate (Fig. 2, 208, contact with precursor gas mixture B at the second temperature; one or more additional precursor gas mixtures comprising PH3, [0014]). (it should be noted that substituting (HF) for (HCl or HBr) is a simple substitution of one known element for another to obtain predictable results (See MPEP2143)
SAMUELSON further teaches a method of growing nanowires (NWs) (Figs. 6/9d, a method of producing a nanowires, [0005]), wherein the growing GaP NWs comprises (Fig. 9d, 14, i-GaAs (second segment) nanowire, [0079]): stopping the flow of the phosphine and aluminum-containing vapor to the substrate (surface termination process comprising Indium, the substrate is heated to 350 oC., and exposed to a flow of TiMnIn for 2 minutes [0065]); and flowing a phosphine and gallium-containing vapor to the substrate (subsequently, a GaAs nucleation layer is grown by introducing a flow of TMGa for 5 seconds followed by a flow of both TMGa and AsH3 for 10 seconds, [0065]). (it should be noted that substituting (TMIn for TMAl) and (GaAs for GaP) is a simple substitution of one known element for another to obtain predictable results (See MPEP2143)
SAMUELSON2 further teaches the method ([0036-0037]), wherein the step of growing the GaP NWs (Fig. 5, 52, first level nanowhiskers, [0074]) comprises: stopping the flow of the aluminum-containing vapor to the substrate ([0059], [0076]; it should be noted that substituting (gallium-containing vapor, indium-containing vapor) for (aluminum-containing vapor) is a simple substitution of one known element for another to obtain predictable results (See MPEP2143)); and flowing a phosphine-containing and gallium-containing vapor to the substrate (PH3-TMG, [0059]).
ROBBINS as modified by SAMUELSON, WEMAN, SEIFERT, and SAMUELSON2 does not disclose the method, wherein the growing GaP NWs comprises: flowing an acid comprising HCl or HBr to the substrate.
YI teaches the method (Figs. 1-2, 100/110, method to grow a nanowire of a semiconductor material, [0018], [0025]), wherein the growing GaP NWs (Fig. 3F, 170, nanowires) comprises: flowing an acid comprising HCl or HBr (Fig. 2, 112, pass a gaseous etchant over the substrate; etchant comprises at least one of a halogenated hydrocarbon (e.g., CBr4, [0051]) and a hydrogen halide (e.g., HCl or HBr [see Claims 6, 16, 22, 28 and 30]) to the substrate (Fig. 3F, 120).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention (AIA ) to have ROBBINS as modified by SAMUELSON, WEMAN, SEIFERT, and SAMUELSON2 to incorporate the teachings of YI such that the method, wherein the growing GaP NWs comprises: flowing an acid comprising HCl or HBr to the substrate, so that the process produced an embodiments of nanowire, 170 was typically with an optimum length in 1-2 micrometer and the diameter of nanowire was typically about 10-25 nm when grown using a 10-20 mm diameter gold nanoparticle, 130 (YI, [0053]).
Regarding Claim 17, ROBBINS as modified by SAMUELSON, WEMAN, SEIFERT, SAMUELSON2 and YI teaches the method of claim 16.
YI further teaches the method (Figs. 1-2, 100/110, method to grow a nanowire of a semiconductor material, [0018], [0025]), wherein after the step of flowing the phosphine- containing and aluminum-containing vapor (Fig. 2, 112, pass a gaseous precursor mixture; precursor mixture comprises a constituent element to the semiconductor material; trimethylindium (TMI) as the precursor comprising indium, and phosphine (PH3) as the precursor comprising phosphorous, [0050]) is stopped, the step of flowing the acid occurs (Fig. 2, 112, pass a gaseous etchant over the substrate; etchant comprises at least one of a halogenated hydrocarbon (e.g., CBr4, [0051]) and a hydrogen halide (e.g., HCl or HBr [see Claims 6, 16, 22, 28 and 30]); for a time period of at least 10 seconds, before the step of flowing the gallium- containing vapor begins (Figs. 2-3, 112, the flows of phosphine and arsine into reactor, 152 were alternated while the flows of TMI, CBr4 and the carrier gas were maintained constant; a routine of a phosphine flow for 20 seconds and an arsine flow for 10 seconds was repeated 50 times, followed by a final phosphine flow for 20 seconds, [0053]; a halogen-free precursor, such as trimethyl gallium (TMG) may be substituted for one of the halogen-containing precursors exemplified above, [0055]). [it should be noted that substituting (indium- containing phosphine vapor) for (aluminum-containing phosphine vapor) is a simple substitution of one known element for another to obtain predictable results (See MPEP2143)].
Regarding Claim 19, ROBBINS as modified by SAMUELSON, WEMAN, SEIFERT, SAMUELSON2, and YI teaches the method of claim 17.
ROBBINS further teaches the method (Figs. 24/25, method for preparing nanowires, [0060]), further comprising: removing (Fig. 10, method 1000 involves the use of a sacrificial portion of a nanowire to provide more effective removal of the nanowires, [0166]) the GaP NWs (Figs. 10/11, 1120, desired portion of the nanowire) from the substrate (Fig. 11, 1140) separating the GaP NWs (Figs. 10/11, 1120, desired portion of the nanowire) from the AlP stubs (Figs. 10/11, 1110, sacrificial portion of the nanowire) using sonication (Fig. 10, current removal of nanowires, methods include using ultrasound and mechanical shearing, [0164-0165]) or a polymer matrix (Fig. 8, 806, after processing the nanowires on the growth substrate, the nanowires can be removed from the substrate by coating the nanowires with a polymer to form a composite, and then removing the nanowires from the substrate, [0150], [0154]); and selectively etching the AlP nanowire stubs to remove the AlP nanowire stubs (Fig. 10, differentially removed by using wet etchant with a etching rate that is significantly higher for the material within the sacrificial than for the material within the desired portion [0173]) from the substrate (Fig. 11, 1140).
(See also additional note in Claim 1, regarding equating sacrificial portion of the NW and the desired portion of the NW of ROBBINS with actual semiconductor materials of SAMUELSON as annotated in Figure 11 and Figure 9d respectively).
Regarding Claim 20, ROBBINS as modified by SAMUELSON, WEMAN, SEIFERT, SAMUELSON2, and YI teaches the method of claim 19.
ROBBINS further teaches the method (Figs. 24/25, method for preparing nanowires, [0060]), further comprising reusing the substrate (substrate can be used repeatedly for nanowire growth, [0207]) to repeat at least 3 times (a recycling process in the production stage can be used, [0092]) the steps of depositing the gold particles (Fig. 24, 2406/2412, nucleating particles, suitable metal catalysts/liquid alloy droplet, colloids comprising Au, or In, [0024]), growing the AlP nanowire stubs (Fig. 24, 2408, AlP nanowires, [0071]), and growing the GaP NWs (Figs. 10/11, 1120, desired portion of the nanowire).
WEMAN further teaches a method of growing nanowires (NWs), (VLS method, e.g. MBE, or MOVP, growing of semiconductor nanowires involve metal catalysis, [0124]), further comprising performing the indium flush (a Ga/In flux can be supplied to the substrate surface, [0099]).
(See also additional note in Claim 1, regarding equating sacrificial portion of the NW and the desired portion of the NW of ROBBINS with actual semiconductor materials of SAMUELSON as annotated in Figure 11 and Figure 9d respectively).
Claim(s) 18 is/are rejected under 35 U.S.C. 103 as being unpatentable over ROBBINS, in view of SAMUELSON, further in view of WEMAN, further in view of SEIFERT, further in view of SAMUELSON2, further in view of YI, and further in view of Daniel Jacobsson et al, (hereinafter JACOBSSON), NPL: Crystal Structure Tuning in GaAs Nanowires using HCl, Daniel Jacobsson, Sebastian Lehmann, and Kimberly A. Dick, Nanoscale, 2014, 6, 8257-8264.
Regarding Claim 18, ROBBINS as modified by SAMUELSON, WEMAN, SEIFERT, SAMUELSON2, and YI teaches the method of claim 17.
Though YI teaches the hydrogen halide and indium-containing vapor comprises phosphine (PH3) and trimethylindium (TMI) precursor substituted with gallium containing vapor comprises (TMGa), [0055], ROBBINS as modified by SAMUELSON, WEMAN, SEIFERT, SAMUELSON2, and YI does not explicitly disclose the method, wherein: the acid comprises HCl, and the phosphine-containing and gallium-containing vapor comprises phosphine (PH3) and trimethylgallium (TMGa).
JACOBSSON teaches the method (growth of GaAs nanowires, using MOVPE system, Experimental details section, [Page 8258, Col 1, Line 6]), wherein: the acid comprises HCl, and the phosphine-containing and gallium-containing vapor comprises phosphine (PH3) and trimethylgallium (TMGa) (Experimental details section, 1st paragraph, [page 8258, Col. 1, Lines 6-8]; It is known to the POSITHA that for growing GaAs nanowire, it is recommended to use arsine (AsH3) as a precursor containing TMGa and for growing GaP nanowires, arsine is substituted with phosphine (PH3) precursor). [it should be also noted that substituting (arsine, (AsH3)) for (phosphine, (PH3)) is a simple substitution of one known element for another to obtain predictable results (See MPEP2143)].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention (AIA ) to have ROBBINS as modified by SAMUELSON, WEMAN, SEIFERT, and SAMUELSON2, YI to incorporate the teachings of JACOBSSON such that the method, the method, wherein: the acid comprises HCl, and the phosphine-containing and gallium-containing vapor comprises phosphine (PH3) and trimethylgallium (TMGa), so that the effects of HCl on the crystal structure and morphology of GaAs nanowires with respect to the surface growth and radial growth characteristics for device applications (JACOBSSON, Conclusion section, [Page 8263, Col. 1, Lines 15-30]).
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
US 20130264687 A1 – Figure 1A-1C, [0086]
STATEMENT OF RELEVANCE – The substrate is further washed with a liquid mixture of hydrochloric acid to remove metal contaminants.
US 20060009003 A1 – Figure 5F
STATEMENT OF RELEVANCE – The nanowire growth from the remaining catalyst islands of the underlying thin film.
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
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/SESHA SAIRAMAN SRINIVASAN/ Examiner, Art Unit 2812
/CHRISTINE S. KIM/ Supervisory Patent Examiner, Art Unit 2812