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1. REPORT NUMBER GOVT ACCESSION NO.S.3ALIPI NT*S CATALO~G NUMdIER

Technical Reporvz No. 80-5 7 C114rIrm-~id SýWils)

RED3,.

.Semiconducting andItli -hia - } Inerim(CR) 1 anid its Derivatives.,,~hncl~e't

- 5 RFORI4ING ORG. REPO0r1'-U`RMUE

7. AUTHOR(s) -. CONTRACT"O GRANT NUMBER(&)

A-a amdal Alan J. Iueegerl NOW14-75-CT9627

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11.KEY WORDS (Contginue, an reverse side If nec*&&e7 and identity by block am~bee.)

-Ilustrous, silvery, flexible, poly ýygstalline f il sp.Lprt.ia1.. alignment iof (CHI) xfibrils, fibrils, low density "foam-like" (CH), c:Ls and trans (CII) ,n and p

Y ~type dopants, semiconductor, organic metal, el2-t-.ochemical doping, (CHi) asanode, iodinated and brominated film, (As2 F~g rechargeable storage batteries,polycarbonium ion chains, polycarbanion, pho ooacefect and photovoltaic 0

20. ADSTRACT (Contlnt eon rWevese side iffnacessary and identity' by bleck atatibr)

Polyacetylene, (CR)I,fis the simplest possible conjugated organic polymer and istherefore of sec iaf undamentidl- teest. It can be pr-epaY~7r-6i ~the form of

0- lustrous, silvery, flexible, polycrystalline films having any desired cis/trans

C>content by catalytic polymerization of gaseous acetylene, 2 ~ The cis-richC.) films can be stretched easily at room temperature in excess, ot (CH) fibrils.

Dark red gels of toluene in (CH) may be prepared using a lower catalyst concen-

Li-I tration. Highly porous,.very low density, "foam-like" (CR) can be obtained fro-.. these gels. Both cis- and *trans (CH)g arz p type RcimieendJ.8utre -hz-a be

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OFFICE ~ ~ ~ OFNVA ESAC

OFFMICEONAAL REPORTAN.C80

Semiconducting and Metallic Covalent Polymer5

(U") x and its Derivatives

by

Alan G. MacDiai'mid and Alan J. Reeger

To be presented

at the

ACS MeetingStzn FranciscoSeptember 1980

4Department of Chemistjy andDepartment of PhysicsUniversity of PennsylvaniaPhiladelphia, Pa. 19104

July 8, 1980

Reproduction in whole or in part is permitted forany purpose of the United States Government

Approved for public release; distribution unlimited.

~ -

"r •' . --"'"ACS- MEETING, SAN FRANCISCO, SEPT. 1980 II• 'SEMICONDUCTING AND METALLIC COVALENT POLYMERS:.. (CH)x AND ITS DERIVATIVES.*

Alan G. MacDiarmid and Alan J. HeegaiDepartments of Chemistry and Physics

University of PennsylvaniaPhiladelph•ia, Pa. 19104

\

Polyacetylene, (CH), is the simplest possible conjugated organic polymerand is therefore of special fundamental interest., It can be prepared in theform of lustrous, silvery, flexible, polycrystalline films having any desfrdci/ans content by catalytic polymerization of gaseous acetylene,CThe cis-rfch films can be stietched easily at room temperature in excess ofthree times thpig original length with concomitant partial alignment of the(CH)"' fibrils.' Dark red gels of toluene in (01)"'may be prepared using alower catalyst concentration.1 Hhl porous, veryx'low density* "foam-.like"(CH!)/I can be obtained from these gels. 7 Both cis- and tran-(CH)"are..2:type

semilonductors 8 which can be treated with a variety of 2- or n-type dopantswith concomitant increase in conductivity to give a series of semiconductorsand ultimately, "organic metals." This report will be directed primarilytowards a description of the more chemically oriented aspects of (CH)r and itsderivatives.

1. Doping of (CR) Films

The various types of dopants and doping procedures, the nature of the(CH) ,chain, and the nature of the dopant in the films will be described below.The ferms "cis" and "trans" used in' conjunction with a doped film will referto the principal isoveric composition before doping and does not imply that

I the isomeric composition either remains constant or changes during the dopingprocess.

1.1. p-Type Doping

1.1.1. Dopants and Methods of Doping. When either cis or trans films are.exposed to the vapor of electron-attracting substances (Z-type dopants) suchas Br , I, AsF , H SO, 9YCIO, etc. 9 ,I 0 they become "doped" with the speciesand t~ir electrical (Table I) and optical 1 2 properties change markedly.

TABLE I

SDOPANTS FOR (CH) .'b 'Conductivity

_ .; ~(ohm-loe-Z•".' :,'25 %C

___ 1.7 x 10-

•', •trans-[CH(r) 4,.]4 x 10-5A. p-Type (Electron-Attracting) Dopants.

-u. rans-[CH(Ht 7 x 10-

l: )trans-[CCHr^ 1• 1 X 10"

0.02 x0

1%•' - uIr"a .cs-[CH~irl0.23]x x 101

11L i| S(Continued)

F..

TABLEI (Continued)

trans-ECRI 0 2 0 ] 1.6 z 1020-(r.20]x 4.0 x 102

trans-[Cr(AsF5 ) 0 .1 0]X 4.0 x 102

Lis-[CH(AsFsoo]€ 1.2 x 103Sis-)0.10]xc ca. 7 Yz 102si-sP*-IH I •. (AsF 6) 0.10]X 40z1

s-[CH(;bF 6)0.05]x4.0: 102

qs-[CH(PF 6 )0.033]x ca.2.5 x 101

cis-rCH(SbCI 6 ) 0 o0 0 9 ]x 1 X 10-

.is-[CI(SbCl 8 ) 0 . 009 5]x I X 101cLs-[CH(SbC15)Q0. 0 2 2 ]x 2

cis-[CH(BF)o. 0 9 ]i x 102.2 0.09(S d X7 x10 2

-cs3soHF)y]X 9.7 X uo2

is-ICH(Cl04 ) 0 .0 6 4 5 Jx Z

is-[CH(sF4) 0 .0 7 7 ]x 2.0 X 10'

Ci8s-[C i.011(AsFs0H)l0.11]x ca. 7 x 10

cis-(CH 1 .0 5 8 (PF5 0H) 0 .0 5 8o]xe . 3 : iO

Cis-[CH(H2S0 4 )0.1C 6 (H20)0.7 O1x 1.2 x 10 3

cis- I CH(HCO4) 0. 1 2 7 (H2 0) 0. 2 9 7 1.2 z

B. n-Type (Zlectron-Donating) Dopants.,i k.-71Lo.30¢cm) ,X2.0 X 1O0

cis-[(Na 0 .21 (CH)]X 2.5 101

,1..1is-7zO1 l(cR) 1 5.0: .0(

trans(Nao-2 8 (E)]x 8.0 X 10

a) 'cis" or "trans" refers to the pu•;i.cipal isomeric compositioni beforedoping.

b) composition by elemental analysis except where stated otherwise.c) composition by weight uptake.d) dopant used: (SO F) 2 . No composition or analysis given. Anderson, L.R.,

Pez, G.P., and Bsu, S.L.: 1978, J.C.S. Chem. Comm., pp. 1 0 6 6 .e) by electrochemical doping using [(n-C4 Hq ) N] [PF . Nigrey, P.J., MacDi-

armid, A.G., and Reeger, A.J.: 1979, anpuglished observations.

Dopant pressures <1 Corr are usually satisfactory. With many dopants the con-duct!,vity increases rapidly through the seiic~nducting regime to the metalliccegime. The "concentrations of the dopants given in Table I are generally themaximum or close to the maximum value readily obtainable. Doping can be ter-.minated at any degree of. lower doping level desired, with corresponding lowerconductivity.

+ +0SSalts containing the (NO)+ or (NO2 ) ions also act as good dopants. Forexample, the PF6 group can be introduced readily into (CH) simply by treatinga (Ca) film (ca. 85% cis isomer) with a CH NO -CH CI solution of tha appru-

prlate salt. Thus, (No2)( lFe ) w yields gol en, flexigle, highly conductingfils of [-(6)0 X, (Tagle I) with liberation of N, vi.,

• , __,. .. ... . -. 1 .. .. . . 4,1

(CS) •'+ 0.033x(N0)+(PF 6)- [C.(PF6 ) 0.033]x + O.O33xNO2

It has been found very recenrly that (CH) films may be doped electrocham-ically either to the semizonducting or metallic regime.13 This is a most im-portant development since it opens: up a general, very simple, readily con-trollable means oZ doping with a-wide variety of species which can not be in-troduced by any obvious conventional chemical means. For example, it wasround that when a strip of (CH) film (ca. 85% cis-isomer) was used as theanode in the electrolysis of aqueous 0.5M KI solution with a potential of 9 V.it was doped during ca. 0.5 hour to the metallic state, to give, by elementalanalysis (CHI 7) -. It is important to note that the flexible, golden-sit-.very films conka?=e• no oxygen (total C, H, and I content-99.8%) and hencehad undergone no hydrolysis and/or oxidation during the electrolytic dopingprmcess. When the (CH) was used as the anode in the electrolysis of 0.5M[(n-C H ).N]+[CIO0- in cH.aCl at 9 V., doping occurred during ca. 1 hour togive tighy conducting (Tanle I), flexible films which, by elemental analysis,had the composition (CH1(004)0 064 1l3 Lower doping levels obtained duringshorter electrolysis times gavey maerial ha-ving conduct:!ities in the semicon-ductor region. 0imilar results were obtained by the electrolysis of methylenechloride solutions if [(n-C H ) AN]+[SO CFF]- and [(n-C H7 ) NH] [AsF ] both ofwhich gave highly conducting goiden-sijvery flexible fE7 s3 The former isassumed to contain the (SO3 CF3 ) and the latter, the (AsF ) species, since le-lmental analysis of the film gave a composition corresponAing to[CH(AsFO)n0 77] . The (AsF 4 ) is probably fopmed by a reaction sequence iii-volving proton lbstraction from in-C3HC3 NH) 1 by fluorine atoms from AsF 6during the electrolysis process.

Rechargeable storage batteries having a high energy density per unit massbave been constructed from single (ca. 0.1 um thick) pieces of (CH) film con-taining LiI sandwiched betwea two pieces of Scotch tape. Values of Vo andI"c up to 3.0 V aud 5 mA/cm2, respectively, have been obtained. Q

1.1.2. Nature of the (CH) Chains and Dopant Species. Raman studies showwhere X-Br or I at least a significant portion of the halogen being presink

as the X3 ion. The halogen partly depopulates the pi bonding system andoxidizes the (CH)x to a polycarbonium ion chin. This-conclusion is supportedby carbon ls core shifts from ESCA studies. The (NO)+ ions are also excel-lent species for Oxidizing the pi eystem of (CH) and are capable of concomi-tantly introducing anions which stabilize the pofycarbonium ion c',alns. 1 0

For example, the [H(PF 6 species liven in equati.on (1) is more appro-priately fo~mulated as [C." u (rF6 ) 033

T'he most simple and general method for simultaneously oxidizing the (CH)xpi system and introducing stabilizing anions appears to be that involvingelectrochemical doping. 1 1 Thus, species such as [CH(ClO ) In4 5 ]x,[CH(AsF , etc. formed electrochemically as descreýoedc nSction 1.1.1.are bel4e2'Zo'contain the (ClO ) and (AsF 4 ) ions, respectively, althoughthe extent. to which charge transier to the anionic species occurs may be ex-pected to vary according to the nature of the dopant. It is interesting tonote that AgC1O4 has also been found to dope (01) f4.lms with (l.0 4 ) ion,

although to lower conductivity levels 1 6 (ca. 3 oAne-cm-1 ) than that obtainedwith eleccrochemical doping.. Tne-.resulting-film is contaminated- with metallicsilver-. In thia case, the Ag+ ion acts as the oxidizing agent, .viz.,

~~+ .,. :(.+ - 1 0(~ •) .l~ + 0.018Ag (2)(cl) + 0.018xAgClO4 *[CH) 4l 0 018 +

Although most studies of (CH) have been carried out on AsF - or I -doped'films, the actual chemical form if which the AsF exists in the film Ls stillnot completely clear. When (CH) film is treatel with very pure AsF5 vapor in

,x.

ra vacuum line pretreated with AsF 5 , elemental analyses for C, K, As'and F give

"an arsenic to fluorine ratio of 1:5 (Table I).17,I1 The sum of the elementalanalyses is 99.7% or better and hence the film contains no significant amountsof oxygen. Photoelectron spectroscopy also shows the pjncipal arsenic spe-cies contains arsenic and fluorine in the ratio of 1:5. ý.ince epr'9 andmagnetic susceptibility studies2O show the paramagnetic radical anion, AsF 5is not present, it seems that the AsF5 might. be in the form of the previouslyunreported diamagnetic (As F .)-2 ion. If the [CH(AsF 5 )] film is treatedeither with AsF5 vapor coniala ing HF or is immersed in Y4f% aqueous HF, thenelemental anal es for C, H, As and F give an arsenic to fluorine ratio of1:6 (Table 1).15 Again, the sum of the elemental analyses for all elements isgreater than 99.7%. If, on the other hand, the [CH(AsF 5 )] film is pumpedfor many hours in a vacuum system containing possible traes of air, elementalanalyses corresponding to [CH1 (AsF 5 OR) ]O , (Table I), are obtained. Zn thisrespect, it might be noted thit many sal~sxcontaining the [AsFS(OH)] ion areknown. The conductivity of all three types of species is essentially identi-cal. These experimental observations are consistent with the reactions below:

(CE(sF) J+ yHsF yx(3)

(•)x + YASF5 CH [(AsFSyxO

ECH(e 1(AsF +yF [HY 6 Y (4)

[CH(AsF5)ylx + yH2 0 Y (CHI•(ASFsOH)y1 (5)

The weak protonic acids, HF and HOH, can be regarded as combining with the

AsFP species to give the strong protonic acids, 'R+(AsFP)-" and 'V(AsF5OH)",respectively, which then dope the (CH) poition of the material according toequations (4) and (5) 17 X

Other investigators have shown on the basis of X-ray absorption and infra-red data that AsFs-doped film, of unknown elemental composition, contains theAsF 6 ion.2 1 This is in no way inconsistent with the above conclusions basedon elemental analyses; indeed, it supports the formulation of the

, [ +Y(AsF)-] species given above. However, these investigators suggestt iztihe ion arises through the reaction below which involves dispro-portioaation ot the AsFs5 •

Mi + 3yx (6C)Xci + Pys5 CH (R'(ABF 6)2y~x + yAsF 3 (6

cs)s21Since AsF is readily removed by pumping, the resulting material should al-ways contain arsenic to fluorine in the ratio of .1:6. This is in conflictwith the elemental analytical data for the [CH(AsF ) ] material. Since[CQ(AsF ) ] decomposes therm. Ily with the liberato of gaseous HF and AsF0,it is als6 •uite possible that [CH(AsF ) ] could be converted to 30

CH +Y (AsF)] according to equation ý4y fy the HF so formed under certaincond1iions oj Landling or storage of the AsFs-doped films.

1.2. n-Type Dopiny

Electrojrdonating, i.e., "-,-type" dopants, may also be introdu,-'ed into A(CH) films (Table I) simply by immersing the film in a THF solution of.Xe.g., sodium naphthalide, viz.,

(.)x + 0.2lxNa Npth E (Na0 2 1 CCH)]x + .2lxNpth (7)

& very large increase in conductivity is noted but it is not as great as that

.observed with most .-type_ dopants.. Alkkli metalS -yals" be introfdtced byfor example, allowing - liquid sodium/potassium alloy at room temperature, ormolten potassium to contact a (Ci)x film. 2 3 A liquid sodium amalgam will al-so Na-dope the film at room temperature. 2 3 Preliminary experiments indicatethat the (CR) pi system may also be reduced electrochemically to give n-typedoping by, for example, the electrolysis of a solution Lit in TRF usinPal(CH) film as the cathode, to give [Li+(CH)-Y] films.1

X y x

The (CH) chain in these materials may be considered as a polycarbanionassociated wIth the corresponding D& metal ion. They are extremely sensitiveto air and moisture. This appears to be a direct result of the anionic na-ture of the (CM) chain and is not directly related to the presence of themetal ion. ThusXit seems likely that all n-doped (CH) will be highly reac-tive regardless of the attendant metal ion, which of course is stable to airand water. Treatment of Na-doped (CH) with D2 0 results in partial hydroge-nation of the carbon-carbon double bopts.1r

2. Synthesis of Substituted Polyacetylines

When ca. 85Z cis films of (CH) are doped with bromine to compositionssuch as [CB3r 3 ] and then partly dehydrobrominated at 150"C, they yield newsemiconducting polymers in which up to 20% of the R atoms have been replacedby Br. They have the approximate composition [CH Br ] e.g.,[CH,,,,Br, .1] . These can then be doped with IloY AXFx to yield new highlycon uc- ing organic metals such as [CH?,!Br 0 n0912 12 and[CH0 .82Br 0 .1 3 (ASF 5 ) 0 .1 2]x, respective .

3. Photoelectrochemical Reactions at Polyacetylene Interfaces

A chemical reaction involving a reduction process, e.g.,

,$-2 +2e- 2S- 2 (8).

can take place with the concomitant production of an electric current when a2-type (CH) film, immersed in a solution containing the oxidized and reducedforms o04 an appropriate couple, is irradiated with light of appropriate wave-length. In the case of the"polysulfide system, the reverse (oxidation)process,.

2S- - S 22 +2e (9)

will take place Simultaneously at the counter electrode, e.g., Pt, which isnot irradiated. The ions produced at a given electrode then diffuse to theother electrode and become available for reuse at that electrode. The pro-cess is, therefore, continuous as Ion he (CH? electrode is irradiatedwith light of appropriate wavelength. , A definite photovoltaic effectcan be observed (V -0.3 volts under illumination of ca. 1 sun) if a fairlythick film of trans-(CH) is used in order to reduce somewhat the otherwisehigh resistance of the (61) electrode. By using a different cell configura-

* " tion, d~scribed in detail efsewhere, 24 ,25 an open circuit current of ca. 40 Uamps/cm may br. obtained. This will undoubtedly be incrsa.ed by, using par-tially doped ýCR) and thinner films. Since (CH) is a P-type semiconduc-tor, photogenerated electron-hole pairs become separated at the (c.) -elec-

trolyte interface and electrons are injected into the electrolyte.

Preliminary experiments have been carried out 2 4 using aqueous solutionsof the couple

SO3 -2 + 201- + R2 0 + 2e+e (10)with qualitatively similar results. It therefore seems highly likely that it

should be possible to fabricate a variety of photovoltaic cells using (Cli)

-.. : + , - .-+.. -i,

-7. -7ZZ

" electrodes immersed in aqueous or nonaqueous solutions of appropriate redoxcouples.

4. Conclusions

It can be seen clearly that (CH)x is quite remarkable in that Its conduc-tivity can be readily modified to span an extraordinarily large range. Con-sidering possible polyacetyle-ne derivatives, replacement of some or all ofthe hydrogen atoms in (CH) with organic or inorganic groups, copolymeriza-tion of acetylene with other acetylenes or olefins, and the use of differentdopants should lead to the development of a large new class of conducting or-ganic polymers with electrical properties that can be controlled over thefull range from insulator to semiconductor to metal. Furthermore, there isconsiderable potential for the possible application of parent or doped (CH)to the fabrication of various types of electronic devices, solar cells, etc.

5. Acknowledgment

This work was supported principally by the Office of Naval Research.

6. References

1. H. Shirakawa and S. Ikeda, Polym. J., 2, 231 (1971).2. H. Shirakawa, T. Ito, and S. Ikeda, Polym. J., 4, 460 (1973).3. T. Ito, H. Shirakawa, and S. Ikeda, J. Polym. Sci. Polym. Chem. Ed., 12,

11 (1974).4. T. Ito, H. Shirakawa, and S. Ikeda, J. Polym. Sci. Polym. Chem. Ed., 13,

1943 (1975).5. M.A. Druy, C.-R. Tsang, N. Brown, A.J. Heeger, and A.G. Macfiarmid, J.

Polym. Sci. Polym. Phys. Ed., 18, 429 (1980); H. Shirakawa and S. Ikeda,ACS/CSJ Chemical Congress, Honolulu, Hawaii, April 1-6, 1979.

6. Y.W. Park, M.A. Druy, C.K. Chiang, A.G. MacDiarmid, A.J. Heeger, H. Shi-rakawa, and S. Ikeda, J. Polym. Sci. Polym. Lett. Ed., 17, 195 (1979).

7.. G.E., Wnek, J.C.W. Chien, F.E. Karasz, M.A. Druy, Y.W'. Park, A.G. Mac-Diarmid, and A.J. Heeger, J. Polym. Sci. Polym. Lett. Ed., 1_7, 779(1979); F.E. Karasz, J.C.W. Chien, R. Galkiewicz, G.E. Wnek, A.J. Heeger,and A.G. MacDiarmid, Nature, 282, 286 (1979).

8. Y.W. Park, A. Denenstein, C.K. -i--ang, A.J. Heeger, and A.G. MacDiarmid,Solid State Commun., 29, 747 (1979).

9. C.K. Chiang, M.A. Druy, S.C. Gau, A.J. Heeger, E.J. Louis, A.G. MacDiar-"mid, Y.W. Park, and H. Shirakawa, J. Amer. Chem. Soc., 100, 1013 (1978).

10. S.C. Gau, J. Milliken, A. Pron, A.G. MacDiarmid, and A.J. Heeger, Chem.Comm., 662 (1979).

11. C.K. Chiang, Y.W. Park, A.J. Heeger, H. Shirakawa, E.J. Louis, and A.G.MacDiarmid, J. Chem. Phys., 69, 5098 (1978).t

12. C.R. Fincher, Jr., M. Ozaki, M. Tanaka, D.L. Peebles, L. Lauchlan, A.J.Heeger, and A.G. MacDiarmid, Phys. Rev., 20, 1589 (1979).

13. P.J. Nigrey, A.G., MacDiarmid, and A.J. Heeger, Chem. Comm., 594 (1979).14. S.L. Nsu, A;J. Signorelli, G.P. Pez, and R.R. Baughman, J. Chem. Phys.,

69, 106 (1978); S. Lefrant, L.S. Lichtmann, H. Temkin, D.B. Fitchen, D.C.Miller, G.E. Whitwell, II, and J.M. Burlitch, Solid State Commun., 29,191 (1979); I. Harada, M. Tasumi, H. Shirakawa and S. Ikeda, Chem. Lett.,12, 1411 (1978).

15. W.R. Salaneck, H.R. Thomas, C.B. Duke, A. Paton, E.W. Plummer, A.J.Heeger, and A.G'. MacDiarmid, J. Chem. Phys., 71, 2044 (1979).

16. T.C. Clarke, R.H. Geiss, J.F. Kwak, and G.B. Street, Chem. Comm., 489(1978).

17. A.. Pron, A.G. MacDiarmid, and A.J. Heeger, unpublished observations(1979).

18. A.G. MacDiarmid and A.J. Heeger, " 1Molecular Metals," Ed., W.E. Hatfield,Plenum Press, New York, N.Y., 161 (1979).

19. I.B. Goldberg, H.R. Crowe, PiR. Newman, A.J. Heeger and A.G. MacDiarmid,J. Chem. Phys., 70, 1132 (1979).

ZO. B.R. Weinberger, J. Kaufer, A.J. Heeger, A. Pron, and& A.G. MacDiarmid,

;.• , . •,-,' ' ..• .. ................ A

Phys. Rev. B., 20, 223 (1979).21. T.C. Clarke, R.H. Geiss, W.D. Gill, P.M. Grant, J.W. Macklin, H. Morawitz

J.F. Rabolt, D.E. Sayers, and G.B. Street, Chem. Comm., 332 (1979).22. C.K. Chiang, S.C. Gau, C.R. Fincher, Jr., Y.W. Park, A.G. MacDiarmid,

and.A.J. Heeger, Appl. Phys. Lett., 33, 18 (1978).23. S.C. Gau, A.G. MacDiarmid, and A.J. Heeger, unpublished observations

(1979).24. S.N. Chan, A.J. Heeger, Z. Kiss, A.G. MacDiarmid, S.C. Gau, and D.L.

Peebles, Appl. Phys. Lett., 36, 96 (1980).25. A.J. Heeger and A.G. MacDiarmid, Proceedings NATO ASI on Low DimensionalSolids, Tomar, Portugal, Aug. (1979).

_44

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Professor R. Drago Dr. Richard A. ReynoldsDepartment of Chemistry Deputy DirectorUniversity of Illinois Defense Sciences OfficeUrbana, Illinois 61801 1 DARPA

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