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(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (43) International Publication Date 29 November 2007 (29.11.2007) (51) International Patent Classification: F28F 13/18 (2006.01) B82B 1/00 (2006.01) DOlF 9/127 (2006.01) PCT (10) International Publication Number W O 2007/137095 A3 Los Altos, CA 94024 (US). DEY, Subrata [US/US]; 43433 Laurel Glen Common, Fremont, CA 94539 (US). WACKER, Barbara [US/US]; 18301 Vanderbilt Drive, Saratoga, CA 95070 (US). XU, Yuan [CN/US]; 273 Silverlake Court, Milpitas, CA 95070 (US). BOREN, Arthur [US/US]; 1251 Nancarrow Way, San Jose, CA 95120 (US). OLSEN, Darin [US/US]; 266 Santa M ar garita Avenue, Menlo Park, CA 94025 (US). ZHANG, Yi [CN/US]; 585 West Iowa Avenue, #7, Sunnyvale, CA 94086 (US). SCHWARTZ, Peter [US/US]; 4956 Janet Court, Livermore, CA 94550 (US). PADMAKUMAR, BaIa [US/US]; 1 1 1 Woodleaft Way, Mountain View, CA 94040 (US). (21) International Application Number: PCT/US2007/069080 (22) International Filing Date: (25) Filing Language: (26) Publication Language: (30) Priority Data: 60/800,935 60/862,664 60/874,579 11/749,1 16 16 May 24 October 12 December 15 May 16 May 2007 (16.05.2007) English English 2006 2006 2006 2007 (16.05.2006) (24. 10.2006) ( 12 . 12.2006) ( 15 .05 .2007) US US US US (74) Agents: BEYERS, Robert, B . et al; Morgan Lewis & Bockius LIp, 2 Palo Alto Square, 3000 E l Camino Real, Suite 700, Palo Alto, CA 94306 (US). (81) Designated States (unless otherwise indicated, for every kind of national protection available): AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, CA, CH, CN, CO, CR, CU, CZ, DE, DK, DM, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PG, PH, PL, PT, RO, (71) Applicant (for all designated States except US): NANOCONDUCTION, INC. [US/US]; 1275 Reamwood Avenue, Sunnyvale, CA 94089 (US). (72) Inventors; and (75) Inventors/Applicants (for US only): DANGELO, Carlos [US/US]; 248 University Avenue, Los Gatos, CA 94030 (US). SUHIR, Ephraim [US/US]; 727 Alvina Court, [Continued on next page] (54) Title: CARBON NANOTUBE-B ASED STRUCTURES AND METHODS FOR REMOVING HEAT FROM SOLID-STATE DEVICES 100 Layer 112, with carbon nanotubes H 6 Catalyst H O 2 adhesion layer 108 Diffusion barrier layer 106 1st adhesion layer 104 : C u substrate surface I C u substrate 102 (57) Abstract: Thermally conductive devices including carbon nanotubes for dissipating heat from solid-state devices are disclosed. The nanotube elements of the invention may be characterized using Raman spectroscopy, and accepted or rejected based on the ratio of the D peak to the G peak of the spectrum. The thermally conductive devices may further include a phase change material that increases lateral heat conduction between the carbon nanotubes. RS, RU, SC, SD, SE, SG, SK, SL, SM, SV, SY, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. PT, RO, SE, SI, SK, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG). (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), European (AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HU, IE, IS, IT, LT, LU, LV, MC, MT, NL, PL, Published: — with international search report — before the expiration of the time limit for amending the claims and to be republished in the event o receipt of f amendments (88) Date of publication of the international search report: 24 July 2008 International application N o PCT/US 07/69080 A CLASSIFICATION O F SUBJECT MATTER IPC(8) - F28F 1 3/1 8 ; D01 F 9/1 27; B82B 1/00 (2008.01 ) USPC - 165/1 33; 423/447.3; 977/742 According t o International Patent Classification (IPC) o r t o both national classification and IPC B FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) IPC(8) : F28F 13/18; D01F 9/127; B82B 1/00 (2008.01) USPC : 165/133; 423/447.3; 977/742 Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched USPC : 165/133, 423/447.3; 977/742 - Text search, a s below. Electronic data base consulted during the international search (name o f data base and, where practicable, search terms used) USPTO West (databases PGPB, USPT USOC, EPAB, JPAB), Google Scholar - Search Terms: heat, spreader, sink, exchanger, carbon, nanotube, copper, Raman, titanium, chromium, tantalum, diffusion, adhesion, reduce, bar πer, reduction, penetrate, dope, doping, thermal, nickel, iron, cobalt, catalyst, nanoparticle, seed, resistance C DOCUMENTS CONSIDERED T O B E RELEVANT Citation o f document, with indication, where appropriate, o f the relevant passages US 2005/0046017 A 1 (DANGELO) 3 March 2005 (03.03.2005) para ; , ; ; , Fig 4 , para ; Category* Relevant t o claim N o 2 , 6-12, 19, 20, 24-26, 7 9 -92, 127-1 31, 142, 145, 147, 164-168, 174, 175 1, 2-5, 1 1-18, 21-23, 2778, 93-126, 132-141 , 143, 144, 146, 148-163, 169173, 177-180 U S 2005/00791 18 A 1 (MARUYAMA e t al.) 14 April 2005 (14.04 2005) para ; ; Fig. 15 1 , 29, 30, 39-42, 60, 61, 70-78, 93-126, 130, 133, 143, 144, 149-163, 169173, 177-180 US 5,525,753 A (MENNUCCI e t al.) 1 1 June 1996 ( 1 1.06.1996) abstract; CoI. 1, In 23-24 WONG et al. "Device characterization o f carbon nanotube field emitters in diode and triode configurations" Diamond & Related Materials, Vol. 14, pg. 697-703 (2005) pg. 697, col. 2 , para 2 ; 698, col. 1 , para 1 ; US 2005/0238810 A 1 (SCARINGE e t al.) 2 7 October 2005 (27 10 2005) para ;  1, 3 , 5 , 1 10-126 1, 13-18, 22, 48-59, 115126 21-23, 27, 28 Further documents are listed in the continuation o f Box C * "A" "E" "L" Special categories o f cited documents document defining the general state o f the art which is not considered to b e o f particular relevance earlier application o r patent but published o n o r after the international filing date document which may throw doubts o n priority claim(s) o r which is cited to establish the publication date o f another citation o r other special reason (as specified) document referring to a n oral disclosure, use, exhibition o r other means document published p π o r t o the international filing date but later than the priority date claimed "T' later document published after the international filing date o r priority date and not in conflict with the application but cited to understand the principle o r theory underlying the invention document o f particular relevance, the claimed invention cannot b e considered novel o r cannot b e considered t o involve a n inventive step when the document is taken alone document o f particular relevance, the claimed invention cannot b e considered t o involve a n inventive step when the document is combined with one o r more other such documents, such combination being obvious t o a person skilled in the art document member o f the same patent family "X" "Y" "O" "P" "&" Date o f the actual completion o f the international search Date of mailing o f the international search report 2 8 IVl AY 2008 Name and mailing address o f the ISA/US Mail Stop PCT, Att π ISA/US, Commissioner for Patents P.O. Box 1450, Alexandria, Virginia 22313-1450 Facsimile N o 571-273-3201 PCT Helpdesk: 571-272-4300 PCTOSP 571-272-7774 Authorized officer. Lee W . Young Form PCT/ISA/210 (second sheet) (April 2007) International application No. PCT/US 07/69080 C (Continuation). Category* DOCUMENTS CONSIDERED TO B E RELEVANT Citation o f document, with indication, where appropriate, of the relevant passages Relevant to claim N o 31-42, 62-69, 93-109, 134-141 , 146, 148, 150163, 169-173 43-78, 1 10-1 14 X U et al. "Enhancement o f thermal interface materials with carbon nanotube arrays" Int. J . Heat and Mass Trans., Vol. 49, pg. 1658-1666 (2006). Available online 6 January 2006. Downloaded from www.sciencedirect.com o n 13 March, 2008. abstract; pg. 1658, CoI. 2 , para 1; pg. 1662, col. 1 , para 1 US 2003/0038382 A 1 (COMBS) 2 7 February 2003 (27.02.2003) para ;  Form PCT/ISA/210 (continuation o f second sheet) (April 2007) INTERNATIONAL SEARCH REPORT International application N o PCT/US 07/69080 Box No. I I Observations where certain claims were found unsearchable (Continuation o f item 2 o f first sheet) This international search report has not been established in respect o f certain claims under Article 17(2)(a) for the following reasons 1 LJ Claims Nos because they relate to subject matter not required to b e searched by this Authority, namely Claims Nos because they relate to parts o f the international application that do not comply with the prescribed requirements to such an extent that no meaningful international search can be carried out, specifically Claims Nos because they are dependent claims and are not drafted in accordance with the second and third sentences o f Rule 6 4(a) Box No. H I Observations where unity of i n vention is lacking (Continuation o f item 3 o f first sheet) Bus International S a ch Λ utiiaiiW /ound .multiple .inventions in this. international application, as follows roup I Claims 1-42, 93-T09, 127-148 a nα H5i-173 directed to a n article comprising a pper substrate configured to fit in a recessed cavity, optionally bonded in the recessed cavity, a catalyst layer o n top of the copper substrate and a layer of carbon nanotubes that contact the catalyst layer, wherein the nanotubes are oriented perpendicular to the surface o f the copper substrate, further wherein said copper substrate comprises a thermal spreader and methods for forming devices incorporating said thermal spreader Group Il Claims 43-78 and 1 10-1 26, directed t o a method of cleaning a copper substrate, forming a catalyst layer o n the copper substrate and growing a layer containing carbon nanotubes o n the catalyst, further wherein said nanotubes demonstrate a particular Raman spectrum o r wherein the copper substrate may be used t o compnse a heat spreader Group III Claims 79-92, directed to a n article comprising a heat spreader with a recessed cavity, wherein the cavity is configured to incorporate a substrate with a thermal interface material, and a method of forming such a n article - Please see extra sheet for continuation 1 I NI As all required additional search fees were timely paid b y the applicant, this international search report covers all searchable claims 2 I I A s all searchable claims could b e searched without effort justifying additional fees, this Authority did not invite payment o f additional fees I As only some o f the required additional search fees were timely paid by the applicant, this international search report covers only those claims for which fees were paid, specifically claims Nos 3 I No required additional search fees were timely paid by the applicant Consequently, this international search report is restricted to the invention first mentioned in the claims, it is covered by claims Nos Remark o n Protest [ I | The additional search fees were accompanied by the applicant's protest and, where applicable, the payment of a protest fee I The additional search fees were accompanied by the applicant's protest but the applicable protest fee was not paid within the time limit specified in the invitation N o protest accompanied the payment o f additional search fees Form PCT/ISA/210 (continuation o f first sheet (2)) (April 2007) Internat.onal appl.cafon N o PCT/US 07/69080 Continuation of Box III Group IV Claims 149 and 150, directed t o a method comprising placing a phase change material between carbon nanotubes in a layer of nanotubes wherein the nanotubes demonstrate a particular Raman spectrum Group V Claims 174 and 175 directed t o a method comprising generating heat in a solid state device and conducting at least some heat away from the device via a thermal interface material attached t o a copper substrate bonded t o a recessed cavity in a heat spreader Group V l Claims 176-180, directed t o a method comp πsing obtaining a Raman spectrum from an article comprising a thermal interface material with a layer of carbon nanotubes wherein the Raman spectrum demonstrates particular characteristics useful for determining the quality of the article The Group I claims require the special technical feature o f the carbon nanotubes oriented perpindicular t o the surface of the copper substrate, not required by Groups M-Vl The Group I l claims require the special technical feature o f cleaning a n oxygen-free copper substrate and forming a catalyst layer o n the copper substrate, not required by Groups I and Ml-Vl The Group III claims require the special technical feature of a heat spreader with a recessed cavity configured t o incorporate a substrate with a thermal interface mate πal, not required by Groups l-ll and IV-VI The Group IV claims require the special technical feature of placing a phase change matenal between carbon nanotubes, not required by Groups l-lll and V-Vl The Group V claims require the special technical feature of generating heat in a solid state device and conducting at least some o f the heat away from the device, not required by Groups I-IV and V l The Group V l claims require the special technical feature of obtaining a Raman spectrum from a n article and accepting o r rejecting the article based o n the obtained Raman spectrum, not required by Groups I-V None o f these technical features are common t o the other groups, nor do they constitute a special technical feature in the other groups Some of Groups I-VI share certain technical features However, the shared technical features do not represent a contribution over the prior art of Dangelo (US 2005/004601 7 A 1, 3 March 2005), further in view of Endo (US 2006/006271 5 A 1, 23 March 2006) Dangelo teaches a heat sink which may be formed using copper (para ), wherein the heat sink is mounted i n a cavity (para [001 0]), and comprises carbon nanotubes (abstract) Dangelo further discloses wherein the prior art teaches thermal interface materials comprising carbon nanotubes grown o n a substrate, as well as the growth of carbon nanotubes by commonly known techniques (para ) Although Dangelo does not teach wherein the formation of nanotubes from a catalyst via chemical vapor deposition is a common method Endo teache the formation of nanotubes by such a process (para ) As such, the only other technical commonality linking some, but not all of the claim groups is the demonstration of a particular Raman spectrum by the nanotubes However, Endo teaches using the ratio of two peaks of the Raman spectrum of a carbon nanotube population t o determine the punty of the composition (para ) A s Groups II, III, and V are directed t o broad claims for which the other inventions disclosed in the application constitute only one of a plurality of possible useful embodiments o r means of achieving the aims of the inventions claimed in Groups II, III and V For groups IV and Vl, the inventions, while specific, constitute embodiments o r inventions which are not necessarily related to o r need not be applied t o the inventions of the other groups of the application Therefore, the inventions listed a s Groups I - V l above lack unity of invention under PCT Rule 13 because they do not share a same o r corresponding special technical feature Form PCT/ISA/210 (extra sheet) (April 2007)