nonlinear optical materialsnonlinear optical activity and to improve the physical properties of...
TRANSCRIPT
AD-A198 305
.( A OPICAL WORKSHOP
OF GANIC DAND OLY MERIC
NONLINEAR OPTICAL MATERIALS
sponsored by
THE DIVISION OF POLYMER CHEMISTRY
AMERICAN CHEMICAL SOCIETY
DTICAUJ1 ,6 TQN
MAY 16- 19, 1988
VIRGINIA BEACH, VIRGINIA
S Cdi'FTINF%1OFTHIP,
REPORT DOCUMENTATIO4I PAG6Ela. REPORT SECURITY CLASSIFICATION 1b. RESTRICTIVE MARKINGS
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4. PERFOR~MING ORGANIZATION REPORT NUMBER(S) S. MONITORING ORGANIZATION REPORT NUMBER(S)
&FOR.R-88-.07186a. NAME OF PERFORMING ORGANIZATION 6b. OFFICE SYMBOL 7a. NAME OF MONITORING ORGANIZATION
Amieri can Chemnical Society (If applicable) AFOSR/NC
6c. ADDRESS (City, State, and ZIP Code) 7b ADDRESS (City, State, and ZIP Code)
Polytechnic University Bldg. 410Brooklyn, N.Y. 11201 Boiling AFB, D.C. 20332-6448
Ba. NAME OF FUNDING/ISPONSORING 8b. OFFICE SYMBOL 9 PROCUREMENT INSTRUMENT IDENTIFICATION NUMBER
AFOSR NCAFOSR-88-0221
Sc. ADDRESS (City, State, and ZIP Code) 10. SOURCE OF FUNDING NUMBERS
AFS/CPROGRAM IPROJECT ITASK WORK UNITBoln FWahntn C 03-48 ELEMENT NO. NO. NO. IACCESSION NO.Bo~ingAF, VshngtnDC 032-64861102F 12303 A3
11 TITLE (include Security Classification)
Organic and Polymeric Nonlinear Optical Nhterials
12. ERSOAL UTHO(S)Gerti , D. J. and Tripathy, S. K.
13a. TYPE OF REPORT 13b TIME RED, 14. DATE OF REPORT (Year, Month, Day) 5 PAGE COUNTFinal FRT0ME -88OT05-19-88 8//
16 SUPPLEMENTARY NOTATIONWorkshop on Organi c and Pol ymeri c Nonl inear Opt ical Nbterial s, Mey 16-19, 1988at Virginia Beach, VA.
17. COSATI CODES 18 SUBJECT TERMS (Continue on reverse if necessary and identify by block number)FIELD GROUP ISUB-GROUP nonilinear opt ical mraterial s, second order nonl inear
Iopt ical suscept ibilIi ty, thi rd order nonl inear opt icalI susceptibility, electro-optic, nonlinear optical devices
19. ABSTRACT (Continue on reverse if necessary and identify by block number)
4"tthis Workshop on Organic and Polymeric Nonlinear Optical Nbterials, the latestdevel opment s in the areas of theory, characteri zat ion, synthesi s, mol ecuiar asserrbl ies,and potential device applications for organic and polymeric materials exhibitingnonl inear opt ical behavi or are dliscussed. 1:1 P',:>11.
120. DISTRIBUTION /AVAILABILITY OF ABSTRACT 21. ABSTRACT SECURITY CLASSIFICATION
22a. NAME OF RESPONSIBLE INDIVIDUAL 22b. TELkPHONEo(nclude Area Code) 22c. OFFICE SYMBOL
DD FORM 1473.84 MAR 83 APR edition may be used until exhausted. SECURITY CLASSIFICATION OF -HIS PAGEAll other editions are obsolete. UNCLASS IF IED
INTRODUCTION
The objective if the workshop was to provide a forum for
the sharing of information and the discussion of device
applications in the area of organic and polymeric nonlinear
optical materials. The workshop addressed the issues of
theory, characterization, synthesis, molecular assemblies,
and potential device applications. Multidisciplinary
interactions are vital to the addvancement of research in
this field, and the seventy-six participants included
scientists from the USA, Japan, UK, France, Germany, and
Canada and represented academic, industrial and government
laboratories.
WORKSHOP FOCUS
The workshop focus was divided into five half-day
sessions and addressed the following topics.
Theory: Current theoretical work on nonlinear optical
interactions in organic and polymeric materials was reviewed,
with a focus on understanding the microscopic properties of
these systems and their correspondence to the macroscopic
properties. The value of modelling these systems and the
usefulness of the theoretical projections for determining
structural requirements for enhanced nonlinear optical
activity was discussed.
Characterization: Experimental studies to deteimire the
second and third order nonlinear optical suscept:Ailities of
organic and polymeric systems was discussed. Limiting values
i6'Approvitor publiireleas.1 distribution unlimited.
for device applications derived from characterization studies
were presented.
Molecular Assemblies: Characterization measurements have
been carried out on many materials in a variety of forms to
provide information on structure-property releationships.
Molecular order is essential for second order nonlinear
rUcal effects --.-.d may on.ha... third order effects.
Therefore, control of molecular orientation in these systems
is important. Useful molecular assemblies, including
Langmuir-Blodgett films and electrically poled polymer
systems were discussed.
Synthesis: The synthesis of organic and polymeric systems is
most effective when carried out in conjunction with
theoretical development and characterization efforts.
Examples of how synthetic efforts can be used to enhance
nonlinear optical activity and to improve the physical
properties of materials under consideration for use in
devices were presented.
Device Applications: Discussions addressed the current
status and the future potential of devices utilizing organic
and polymeric nonlinear optical materials.
SUMMARY
The Workshop on Organic and Polymeric Nonlinear Optical
Materials was very successful. The informal atmosphere
encouraged informal discussions, of particular importance in
this interdisciplinary field.
2
A Topical Workshop
ORGANIC AND POLYMERIC
NONUNEAR OPTICAL MATERIALS
sponsored by
The Division of Polymer Chemistry
AMERICAN CHEMICAL SOCIETY
May 16-19, 1988
Virginia Beach, VA
Co-ChairmenDiana Gerbi Sukant Tripathy
The generous support of the contributors is gratefully ack-nowledged: Air Force Office of Scientific Research, Officeof Naval Research, Du Pont Company, Hoechst-Celaneseand 3M Company.
Monday Evening, May 16, 1988
3:00-9:00 p.m. REGISTRATION6:30-9.30 p.m. WELCOMING RECEPTION
PROGRAM:
Tuesday Morning, May 17, 1988
8:15 A.M. Opening Remarks
8:20-9:10 A. "An Overview on Nonlinear Optical Polymer Sys-tems and Devices" by D.R. Ulrich (Air Force Of-fice of Scientific Research)
9:10-10:00 8 . "Nonlinear Optical Effects in Polymeric Films" byP.N. Prasad (State University of New York atBuffalo)
10:00-10:30 Break
10:30-11:20 C. "Recent Advances in Nonlinear Optical Proper-ties of Organic and Polymer Systems" by A.F.Garito (University of Pennsylvania)
11:20-12:10 D. "Conjugated Polymers and Nonlinear Optics" byS. Etemad (Bell Communications)
Lunch
Tuesday Afternoon, May 17, 1988
1:30-2:20 E. "Anisotropy of the Third Order Nonlinear Optical
Susceptibility in Conjugated Polymers" by A.J.Heeger (University of California at Santa Bar-bara)
2:20-3:10 F. "Nonlinear Optics in Ordered Molecular Sys-
tems" by K.D. Singer (AT&T)
3:10-3:40 Break
3:40-4:30 G. "Several Series of Novel Polydiacetylenes forNonlinear Optics" by H. Nakanishi (ResearchInstitute for Polymers and Textiles, Japan)
4:30-5:20 H. "Resonance Effects in Cubic Hyper-polarisabilities of Conjugated Polymers, by F.Kajzar (CEN Saclay, France)
Wednesday Morning, May 18, 1988
8:30-9:20 . "Nonlinear Optical Measurements on LiquidCrystals and Quasi-Liquid Crystals" by Y.R.
Shen (University of California at Berkeley)
9:20-10:10 J. "Nonlinear Optical Effects in Conjugated Sys-
tems" by D. J. Gerbi (3M Co.)
10:10-10:40 Break
10:40-11:30 K. "Optical Nonlinearity: Molecules, Assembliesand Wave Phenomena" by G. R. Meredith (E.I.
DuPont DeNemours and Co.)
10:30-12:20 L. "Characterization of Polymeric Nonlinear Opti-cal Materials" by G. Khanarian (Hoechst-Cel-anese)
LUNCH
Wednesday Afternoon, May 18, 1988
1:30-2:20 M. "Preparation and Characterization of Organo-Transition Metal Langmuir-Blodgett Films" by T.Richardson (University of Oxford, U.K.)
2:20-3:10 N. "Optical Properties of Organized Assemblies"
by S.K. Tripathy (University of Lowell)
3:10-3:40 Break
3:40-4:30 0. "The Nonlinear Optics of Langmiur-BlodgettFilms" by I. Peterson (GEC Research, Ltd., GreatBritain)
Wednesday Evening, May 18, 1988
6:00 p.m. POSTER SESSIONWine & Cheese
8:00 p.m. BANQUET
Thursday Morning, May 19, 1988
8:30-9:20 P. "Advances in Organic Electro-Optic Devices" byR.S. Lytel (Lockheed Research and Develop-ment)
9:20-10:10 Q. "Organic Nonlinear Optical Devices and Mater.ial Considerations" by B.K. Nayar (British Tele-com Research Laboratories, U.K.)
10:10-10:40 Break
10:40-11:30 R. "Towards Nonlinear Optical Applications ofPolydiacetylenes" by M. Thakur (AT&T)
11:30-12:20 S. "High Resolution Laser Spectroscopy in Poly-mers" by D. Haarer (Universitat Bayreuth,West Germany)
12:20 "Closing Remarks" byK.J. Wynne(Office of NavalResearch)
** * *.***.** ** ****..*.****'**** O QQ Q
List of Registrants
"ORGANIC AND POLYMERIC NONLINEAR OPTICAL MATERIALS"
MAY 16 - 19, 1988Virginia Beach, VA
Gregory L. Baker David B. CottsBelicore KRI International331 Newman Springs Road Advanced Materials Lab.3X-275 19-9 Torishima 6-ChomeRed Bank, NJ 07701-7020 Konohana-ku(201) 756-2932 Osaka 554, Japan
(06) 466-2531
David N. Beratan
Jet Propulsion Laboratory Daniel R. Coulter4800 Oak Grove Drive Jet Propulsion LaboratoryM.S. 67-201 4800 Oak Grove DrivePasadena, CA 91109 M.S. 67/201(818) 354-6548 Pasadena, CA 91109
(818) 354-3638Murrae J. BowdenBellcore William Daly331 Newman Springs Rd. Department of ChemistryRed Bank, NJ u,701 Louisiana State University(201) 758-3360 Baton Rouge, LA 70803
(504) 388-3237Michael E. BoyleNaval Research Laboratory John EichelbergerPolymeric Materials Pennwalt CorporationNRL Code 6123 900 First AvenueWashington, D. C. 20375-5000 P.O. Box C(202) 767-2472 King of Prussia, PA 19406
(215) 337-6729Eve ChauchardDept. of Electrical Engineering Susan ErnerUniversity of Maryland LockheedCollege Park, MD 20742 0/93-50 B/204(301) 454-6834 3251 Hanover St.
Palo Alto, CA 94304Paula Cockerham (415) 424-3131Martin Marietta Labs1450 S. Rolling Rd. Shahab EtemadBaltimore, MD 21227 Bellcore(301) 247-0700 Room 3X-291
Red Bank, NJ 07701(201) 758-2942
Warren T. Ford Alan J. HeegerDept. of Chemistry Polymer instituteOklahoma State University University of CaliforniaStillwater, OK 74078 Santa Barbara, CA 93106(405) 624-5946 (805) 961-2001
Keith A. HornRobert P. Foss Allied-Signal Co.E.I. du Pont de Nemours & Co. Engineered Materials SectorCR&D Box 1087RExperimental Station E328/215 Columbia Tpke & Park Ave.Wilmington, DE 19898 Morristown, NJ 07960(302) 695-4367 (201) 455-3022
Anthony Garito Phelps JohnsonDept. of Physics Rohm & HaasUniversity of Pennsylvania P.O.Box 219Philadelphia, PA 19104 Bristol, PA 19007
(215) 785-8552Diana J. Gerbi3M Company Francois Kajzar3M Center Bldg. 201-2E-08 CEA IRDI D. LETISt. Paul, MN 55144 Dept. d'Electronique et(612) 736-2557 d'Instrumentation Nucleaire -CENIS
91191 Gif Sur Yvette CedexFrederick J. Goetz FrancePennwalt Corporation (33)1-69-08-6810900 First AvenueP.O. Box C G. KhanarianKing of Prussia, PA 19406 Hoechst-Celanese(215) 337-6758 86 Morris Ave.
Summit, NJ 07901Robert Gulotty (201) 522-7918Dow Chemical Co.CRIMCL Bldg. 1776 Peter LeungMidland, MI 48674 3M(517) 636-2861 St. Paul, MN 55144
Dietrich Haarer Richard LytelExperimentalphysik IV LockheedPostfach 101251 R-202 D-9720University of Bayreuth 3251 Hanover St.Bayreuth D-8580 Palo Alto, CA 94304Federal Republic of Germany (415) 424-2363(0921)55-3240
Michael HaydenUnisys Corp.P.O. Box 64525M.S. U1L14St. Paul, MN 55164(612) 456-3669
-3-
Robert J. McMahonDept. of Chemistry 6-427 British TeecomM.I.T. R2121Cambridge, MA 02139 British Telecom Research Labs.(617) 253-4546 Martlesham Heath
Michael A. Meador Suffolk IPS TRE, U.K.
NASA Lewis Research Center Moris K. Niknam21000 Brookpark Road Chemical Abstracts ServiceM.S. 49-1 2540 Olentangy River Rd.Cleveland, OH 44136PO.Bx31(216) 433-3228 P.O. Box 3012
Columbus, OH 43210
Gerald Meredith (614) 421-3600
E.I. du Pont de Nemours & Co. Raphael OttenbriteExperimental Station Dept. of ChemistryCR&D 356 Virginia Commonwealth UniversityWilmington, DE 19898 Richmond, VA 23284(302) 695-4984 (804) 367-1298
Joann MillikenOffice of Naval Research Joseph W. Perry800 N. Quincy St. Jet Propulsion LaboratoryArlington, VA 22217 4800 Oak Grove Drive(202) 696-4409 M.S. 67-201
Pasadena, CA 91109
Jovan Moacanin (818) 354-5794
Jet Propulsion Laboratory Ian Peterson4800 Oak Grove Drive GEC Research Ltd.M.S. 122-123 Hirst Research CenterPasadena, CA 91109 Wembley, U.K.(818) 354-3178
Machiro Nakanishi Juergen L. W. Pohlmann
Research Inst. for Polymers & Textiles Dept. of the Army, USACECOM
-1-1-4 Yatabe-Higashi Center for Night Vision
Tsukuba 305, Japan & Electro-Optics
(0298) 54-6310 AMSEL-RD-NV-L, Bldg. #317Fort Belvoir, VA 22060-5677
Piero Nannelli (703) 664-1432Pennwal t Corporation Pamela Porter900 First Avenue Martin Marietta LabsP.O. Box C 1450 . Rolling Rd.King of Prussia, PA 19406 Baltimore, MD 21227(215) 337-6367 (301) 247-0700
-4-
Richard S. Potember Y. R. ShenJHU/Applied Physics Lab. Physics Dept.Johns Hopkins Rd. University of California, BerkeleyLaurel, MD 20707-6099 Berkeley, CA 94720(310) 953-6251 (415) 602-4856
Paras Prasad Kenneth SingerDept. of Chemistry AT&T Engineering Research CenterSUNY at Buffalo P.O. Box 90052 Acheson Hall Pricnceton, NJ 08540Buffalo, NY 14214(716) 831-3026 Karen Stetyick
Johns Hopkins UniversityTim Richardson Applied Physics Lab.Oxford University Johns Hopkins RoadDept. of Engineering Science Bldg. 2, Rm. 252Parks Road, Oxford OXl 3PJ Laurel, MD 20707England, U.K. (301) 953-6242(0865) 273092
Albert E. StiegmanGareth Roberts Jet Propulsion LaboratoryDept. of Engineering Science 4800 Oak Grove DriveUniversity of Oxford M.S. 67/201Parks Road Pasadena, CA 91109Oxford, OXI 3PJ (818) 354-4857England, U.K.
Shao-Tang SunGuerino Sacripante Hercules Inc.Xerox Research Center of Canada Rt. 48 & Hercules Road2660 Speakman Drive Wilmington, DE 19894Mississauga, Ontario (302) 995-3112Canada L5K 2L1(416) 823-7031 Murial Thakur
AT&T Bell LaboratoriesMarcia L. Schilling 600 Mountain Ave.AT&T Bell Laboratories Rm. #6C-312600 Mountain Ave. Murray Hill, NJ 07974R. IA-234 (201) 582-2522Murray Hill, NJ 07974(201. 582-6434 John M. Torkelson
Dept. of Chemical EngineeringPaul J. Shannon Northwestern UniversityNexcules Inc. Evanston, IL 60208at 48 & Hercules Rd. (312) 491-7449VWilington, DE 198941302) 995-3854
-5-
Donald R.- Ulrich Kenneth WynneAir Force Office of National Science FoundationScientific Research Materials ResearchBolling AFB 1800 G Street N.W.Washington, D.C. 20332 Washington, D.C. 20550(202) 767-4963 (202) 696-4410
Maria M. Vida Frederick C. ZumstegChemical Abstracts Service E.I. du Pont de Nemours & Co.2540 Olentangy River Rd. Experimental StationColumbus, OH 43210 CR&D E356-213(614) 421-3600 Wilmington, DE 19898
(302) 695-1485Jane C. VoglDivision of Polymer ChemistryPolytechnic University Accompanying Guests333 Jay St.Brooklyn, NY 11201(718) 260-3125 Mrs. G. Khanarian
Mrs. G. Meredith (Leslie)Otto Vogl Mrs. S. ThakurHerman F. Mark Prof. of Poly. Sci.Polytechnic University333 Jay St.Brooklyn, NY 11201(718) 260-3180
Bruce D. WebberAmoco Technology Co.P.O. Box 400, F-4Naperville, IL 60566(312) 420-4670
James K. WhitesellDept. of Chemistry'University of Texas at AustinAustin, TX 78712(512) 471-1094
C.C. WinterBritish Telecom Research LabsRt 2333Martlesham Heath, IpswichEngland, IP5 7RE, U.K.
"ORGANIC AND POLYMERIC NONLINEAR OPTICAL MATERIALS"
May 16 - 19, 1988Virginia Beach, VA
List of Registrants: Addendum
Jan Bartus Francis WangH.F. Mark Dept. Lawrence Livermore National Lab.Polytechnic University L-250, P.O. Box 808333 Jay Street Livermore, CA 94550Brooklyn, NY 11201 (415) 422-7305(718) 260-3403
Michael A. LeeDept. of PhysicsKent State UniversityKent, OH 44242
T. MookherjiTeledyne Brown EngineeringM.S. 52300 Sparkman Dr.Huntsville, AL 35807(205) 532-2875
Peter Palffy-MuhorayLiquid Crystals InstituteKent State UniversityKent, OH 44242
Wei-Fang SuWestinghouse R&DPittsburgh, PA 15235(412) 256-2096
Laren TolbertGeorgia Institute of TechnologySchool of ChemistryAtlanta, GA 30332(404) 894-4043
Eric Van StylandCREOLUniversity of Central Florida12424 Research ParkwaySuite 600Orland!,, FL 32826(407) 'j8-6814
"ORGANIC AND POLYMERIC NONLINEAR OPTICAL MATERIALS"
May 16 - 19, 1988Virginia Beach, VA
List of Registrants: Addendum #2
William KrugBoeing Electronics High Tech CenterP.O. Box 24969M.S. 7J-27Seattle, WA(206) 865-3033
James Le MayLawrence Livermore National Lab.P.O. Box 808Livermore, CA 94550(415) 422-7305
Edward MiaoBoeing Electronics High Tech CenterP.O. Box 24969M.S. 7J-27Seattle, WA 98124(206) 865-3027
George RayfieldUniversity of OregonEugene, OR 97403(503) 382-4100
Nan-Loh YangChemistry Dept.St. George CampusCCNY50 Bay St.Staten Island, NY 10301(718) 390-7994
Stanley C. IsraelDept. of ChemistryUniversity of LowellLowell, MA 01854(617) 452-5000
A Topical Workshop
ORGANIC AND POLYMERIC
NONUNEAR OPTICAL MATERIALS
sponsored by
The Division of Polymer Cbemistry
AMERICAN CHEMICAL SOCIETY
May 16-19, 1988
Virginia Beach, VA
Co-ChairmenDiana Gerbi Sukant Tripathy
The generous support of the contributors is gratefully ack-nowledged: Air Force Office of Scientific Research, Officeof Naval Research, Du Pont Company, Hoechst-Celaneseand 3M Company.
Monday Evening, May 16, 1988
3:00-9:00 p.m. REGISTRATION6:30-9:30 p.m. WELCOMING RECEPTION
PROGRAM:
Tuesday Morning, May 17, 1988
81 AOpening Remarks
8:20-9:10 A. "An Overview on Nonlinear Optical Polymer Sys-tems and Oevice-"'y D.R. Ulrich (Air Force Of-fice of ScientificReFsearch)
9:10-10:00 B. !- 'Nonlinear Optical Effects in Polymeric Films" byP.N. Prasad (State University of New York atBuffalo)
10:00-10:30 Break
10:30-11:20 C. -'4ecent Advances in Nonlinear Optical Proper-ties of Organic and Polymer Systemsf-,by A.F.Garito (University of Pennsylvania)
11:20-12:10 D. "Conjugated Polymers and Nonlinear Optics" byS. Etemad (Bell Communications)
Lunch
Tuesday Afternoon, May 17, 1988
1:30-2:20 E. "nisotropy of the Third Order Nonlinear OpticalSusceptibility in Conjugated Polymers" by A.J.Heeger (University of California at Santa Bar-bara)
2:20-3:10 F ... "4 onlinear Optics in Ordered Molecular Sys-tems," by K.D. Singer (AT&T)
3:10-3:40 Break
3:40-4:30 r. vrlSeries of Novel Polydiacetylenes forNonlinear OpticgO by H. Nakanishi (ResearchInstitute fr Pol rs and Textiles, Japan)
4:30-5:20 H. flesonance Effects in Cubic Hyper-polarisabilities of Conjugated Polymers, by F.Kajzar (CEN Saclay, France)
Wednesday Morning, May 18, 1988
8:30-9:20 'onlinear Optical Measurements on LiquidCrystals and Quasi-Liquid Crystals'j- y Y.R.Shen (University of California at Berkje*)
9:20-10:10 J "Nonlinear Optical Effects in-Conjugated Sys-tems" by D. J. Gerbi (3Mco.)
10:10-10:40 Break
10:40-11:30 K. epical Nonlinearity: Molecules, Assembliesand Wave Phenomenat!'Py G. R. Meredith (E.l.DuPont DeNemnours-and-Co.)
10:30-12:20 L. ""'Characterization of Polymeric Nonlinear Opti-cal Materials" by G. Khanarian (Hoechst-Gel-anese)
LUNcH
Wedne, 4y Afternoon, May 18, 1988
1:30-2:20 M. "reparation and Characterization of Organo-Transition Metal Lan gmuir-Blodgett Filrnk-by T.Richardson (University of Oxford, U.K.)!
2:20-3:10 N. "Optical Properties of Organized Assemblies"by S.K. Tripathy (University of L-povtell)
3:10-3:40 Break
3:40-4:30 0. "The Nonlinear Optic~ of Langmiur-BlodgettFilms" by 1. Peoterson (G Reerh, Ltd., GreatBritain)
Wednesday Evening, May 16, 1988
6:00 p.m. POSTER SESSIONWine & Cheese
8:00 p.m. BANQUET
Thursday Morning, May 19, 1966
8:30-9:20 P. "Advances in Organic Electra-Op tic Devicesi yR.S. Lytel (Lockheed Research and Develop-ment)
9:20-10:10 Q. "Organic Nonlinear Optical Devices and Mater-ial Consideratiomj 7by B.K. Nayar (British Tele-comn Research Laboratories, U.K.)
10:10-10:40 Break
10:40-11:30 R. "Towards Nonlinear Optical Applications of
Polydiacelylenes" by M. Thakur (AT&T)-,
11:30-12:20 S."High Resolution Laser Spectroscopy in Poly-mergs4by 0. Haarer (Universitat -Bayreuth,West Germany)
12:20 "Closing Remarks" byK.J. Wynne(Office of NavalResearch)
*** .** *** *** *** *** *.* X
A-1
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me. * - . KOP . 1.1 x 10-4 "a
me .
& m. * jDSt 0.41
i0.2
IL Aftoee 00 S.1 0.2 0.3
PON" P#011id OUvfmI
A-S
FUNCTIONALIZATION OF POLY (-IiYDROXY- p i -;F 7:-,'
STYRENE) WITH NLO CHROMOPHORES TIME DEPENDENCE OF d3 o1.2
T0a
0.4-
P 000 12000 24000 :36000 46000
TIMIE (minutes)
Values for X(31, Eg. W From SemlemplricalCalculations and Experimentally Determined
(PS )O-NPP FILMS y(HOMO) 2 Delocallzation Length for PrototypeEFFECTS OF .0NNEAUING Ladder Polymers and Polyacetylene
1.2
C NcL:Pdyuw EgjaV) wfeg X41~ ISOUl
IIPdstu PII IS S 16O- 2
0 0.8 2
- - -7 rJN71 N U A N NC I PuW nd e PXL 31 3. 2 X 10 - 26
00.0
TIMSEte (mnues
A-6
Implications of y(HOMO) 2 Dependence of y(-3w. w, w. w)
Delocalization Experiments For On Chain LengthMLO Polyn'en Synthesis
-ewfee L- %02 PAimns a" asmw aiO Mbe*
*NW 00~sw At wm Nsay Chains. g a IS 06a0 a" 10.
0 adrPaa May be Slv e In U Ope CaiailexSIWAIsaus1 -Imse Wv Odllal Overlso WO
Load to dwd Enh 04e oafttao"sad Red Optical~.
Application of Dalton's Results -t -I.
* Solubl~ed Ladde PQIynee IIy Lewis AcidChwrg Traneler
iRigd is mlwb~
A-7
*LINEAR OPTICAL ANDPUSYNCHEMIC POLymER
THERMAL FFCTECLOM OLYER
CIN SOLID GAS LAUESEARSIY LEDFLS MO DEMAII OCKNEDRT
THERMAL EFFEC PLMERS*f LYERS
LM SOMLD STTELAARTSAT LASERS
STATE LASERSILAPONDMPEDCOVSRY-~~P*O CT SOIESTSET)ER
OIED SWOTCH -~lR * SUE ANCD
- WAVELENGTH RESPONSE10VER VISIELE ANDNEAR 14RI
J RECTION EFFICIENCY
-=E IIEFORE AND AFTERTUNIADE FILTERS WSWITCHING
-HIGH DAMAGETHRtESHOLDS I tW/-I
* Low INSERTION LOSSES_______AND MINIMALt RETROFIT
OPTIAL LIMI1ATER C09APEXITIES
A-8
TIMEFIELD OF VISION
*PROTECT AGAIST RAPIDLY TUNAKlE. PULEDVISILE AND NEAN INO LASER THREATS TO MIGMGAIN OPTICAL SYSTEMS,I ISEPIA FOR RANGSFINOERS. VISUALSENSORS. CAMERAS. AND MOSTIMPOIRTANTLY. THE EYE
Third Order PolYmers forOptical Devices Phthalocyanines
*PlaEr, Slmotur. W~it Exenwea.T btlsIII
M~ - NOAiH
OMSil In Pen Pnm. C4A4LWgad Otf.Ngito SyStem oR Ne16inng with Nueffw Mejiagini,
Lwwas comiaml aLarge NLO response discovered by A. GaritoH4 Aih os"l Timillp SgfaatMe£wog- 11lalf N2 ftlf ASO&" N" *"ilna Numerous variants synthesized to tailor
* znNw SION NLO activity$Onee COGIOWe Fa Thi Fil SaWM Fabrication properties
Opplliriamip00.Nui Pvoeggm,
A-9
Basic Structure of an Optical Neural Network -
Input Plane OpticM: mplmened Output Planeof Neurons Inecnetos of Neurons
"A -- N NX(WI). an ,
Angular Dependence of Reflected X13) forOriented Trans-Polyscetylene by Third
Harmonic Generation Third Order Response in
1.0 Polyacetylene
0.8 0 ResoelI Process
- Pholoaiclied Noodoesi Excitation*s0.6 - Associated 31lruhues 0#61011160,1 11101110111.
filpealmoe. Polere"s Reponible for Large Shifts 01P(3OeclI6etar Siromgb Oboserve With Reomem Pumpng
0.4 - Commosese of Elocilem-Ptwetwe intetac~-Efectreuila AReneni Ea 1ueh
04 -- Nmedlet. Dissiphtion Prodoum, s 6mer
0due so too~ Ino Pum
Transtait or Guide Light
A-1O
Degenerate Four Wave Mixingof Biaxial PUT
Third Order MLO Response of Ordefred P ol.mSrT,, l
Ordered Polymers
C a l ln w 011 d R e d 0 w Pea Fiw I
R d
co*.pabuo utoongJam w
GA- Trees,UnWial PINT - Thid Hanwnmslo - Xto 14
Ganoalie INT
aulial PUT - Degenwmva Few - Xi 10- osew .2" *Wellf Mizng 0.0
(0FWIM -1$ -10 -S a 5 10 1s
UonaleA PRO - 0o900"i Few - XO is X l*-
,, fe. P9
____o____U -_I__. OPWM sign
O RsqmmosS l Film Quiely - Avoid Iah-eomUp Graft or F"ious Romoom bComponets Which 5.8dmr Lgh iNT A-.
0.2 -
-4 -3 -2 -1 0 1 2 3 4 5PS
Nonresonant ThirdOrder Susceptibility X(3 ) in
Blaxial PBT X ( ) Polymers for Fibers0 OoCgoloxute Four We" Mixing
Pr Plot D O
X'4 As aFunevi of Film NmloUn~
o • X' units have modest activity but very
low absorptiona * Polymer backbone conlers secondary properties
- Spinability•Shear and elo~gationlal flow yield alignment
* New Pmalg fox T'N Ouwar Dmoeo Anqimrogia X0 Mmetotl fo Ogfosny.aoa'emd
Ihw nfl ilm AItleauo
A-1l
X43) Materials J OLYALXYLTH IPME
Thin Limit Thick LimitProperties Properties __________
a Near reasonance at Non resonantaHigh n2 *Lower n2*High absorption (a) *Very low absorption 4
Material Mater"a* Phhaloyanees *Side chain polymer
Application Application*Etalons * NLO fibers2*All optical SIM's a All optical switching
Advantages Advantagesa, Fabrication ease a, Fiber spinning easea, Room temperature operation le Potentially highestoa, Potentially highest n 2 materials n2 /a materials2 2345
74. 11k. - ent I= 1484101 si l 554111 few a 20 LaY.?
S. 554 ob 4114V U 6MM Sbe. iA nMO W 412w anenammim ON~e*am as 3"S
OVANUR wllesu
'0lT~I IIYIPI OSASYS wilt
0 Omani lt 011IMM(IW 1111EIII
I.., tClestll AS"f~l ASChS(IIE(MAE 411
o SM~lt'*11? 114i1timlguc SIEMIIOS IItI/
* ~ ~ ~ ~ o tS Uti 1 *1 1 11 (1 5 L C C C o m p o s ite
~ * *.>~. * d-cc (Raytohscanfegmrmtegire)* .Randomly oiseowed LC msctxodropit
1. *Low scatin - hazy blue to tanspareri*Keir malnal with positive n
006
am
am
002
CISW SiOMIOS(5
A-12
ADVANCID POlYFIE MENDS AND OPIICS
Sjhiina ~rohm Oaefiif man 9kufulan nss min
amimot YOgs
o Isuoeoic 0 DOWS AL PIIA[Os0 P0418 0 LADDIea OBtlLlo 0 ORDERED
t1990 - { 5153 - ALLOYS
0 SILUIANDUCES 0 NEAR Off RESONANCE
0 SM I-OIAMliZS 0 PLANS,
PARAtiLL COPPUIh6
AlsolpIioMl I IMWIIS
4OIICULAR (OMIOIPSAIIOIS AND 511(EI
I(VIIOPHIMI Of AtIIIMAiIV[ HllRODOlOIIIS. SUCHN AS 110111 1 I1) APlIIIAIII'
STAt ISIICAl AVERAGING 01 OlI(MIAIog 111(1t GAS MODMIW
IAllSII(Al AVINAGIMS 0f CHAIR t[9uiss
illicls Of IM1useON1CUt~e IMIIMACTIONS O0l Sug~h HOIICWE DIG p#OpIRIjS
(IIICIS 01 Ilt(lNOICUIA IRMACIIOMS 00 PMIICII CONUOtNAIION AMA SIll,( 111of
('F(CI Of IMIit"CHICUlse IMIIAIioOS 00 AMMIA III ASIIIICIUgI
THE KEY: INTERMOLECULAR INTERACTIONS,
A-13
Status of Understanding for State-of-Art X(2) DevicesPolymer Design * Te@-Wave Smede lo*4U -,'a E~lreopll Modulator
Detlesd Sloepie.. Pofyes4m e 1e MIM AeuIn palie Mdlior
Neolbeerswich OV~es AeJy116V436V) 2112-10 112 1.3" Nen*WW OpftPoweeftet No 4' M'W) 0.5-5 0.03ihtiiiwX
" Petental Cmwludmw of 0 OdMisi to NI.O (8.0 Cres.Poe oAem W 056 .3
Froqmue" 4GO 5-24 >60
- Me Expected Veleat fMloww" ig mili Higher Frequency* A Qusalwe Correlaion neriwe. XA we Ekeepop Devices a Poesile With ptyNWOetucafzate Leegls 0 ~Eluei greg Co
" Effect Of DOM 111 ln,.nduli Cht Teft, - High Speed fler Murni P"roes!"nNeed o Cierfiud - 25 OfHi sea Target
SNegeded H5wmmfl Geeeradeu* 6411111110ar Th LadMift to Predi" meweeateuee ihElcinyD.Isg4 idWith Lw" Sftsi a111* nd Thug order (Gaoug-mel4&imLo
melecuie SsespwlUftee
Waveguide Devices
Ste (141 Guide Polymeric Electrooptic ModulatorModulator
mul"llayw td)ouie M adulator
2d ei eq.me (p "am In" OutputFabricationt RenewLngiol Laser Seem SinaOpICuig Cuplgesi. SecondOdo CCoddin .Cu~t
I \ E~lectrodeLaecowsfns ISNIS jAaye
n ~ fl Peltedle xde Film
Comupete Electrod F it Cladd ing
ModIultr Catle Elcod I. aye
All Oudee T~ :siarintion
A-14
Traveling-Wave Waveguide State-of-Art X(3) Devices
54f I -0 Udmiiel *W Out 0 Far tm og m"x4
Liqilt I. * Liwg PaeIf In Mul~pbumig a"d DemollIlnq
- andle Oft" InputaL- vey u" x"'
* CAN Loed #aV- AN 0~aa Inhremaaint pt $Meiia Wch
- 0119a1 911114110001Y eOW We"~ OpOICal Inemfioa
* VOltage Vadmn A"ms fle Length - OPUbyWIW01 ~*A 114 a e&~(I. ; A IteSitadakwp
0 IPate Dvft pam~m0 *11 P-ade0 Palic Oed Oft Musuda Propertit" In a* Imedig Dvic PaameavmCoompllcagad Wey- Von*a" - Spend - n-,IaM~i by nDe Avi£shlci- Opmeca No"e sue - Lenglis - ParalfeaUAaelog P'eaung of 20 Imag- Of*ve Power - Impeae - PDee Caguge OtimM anme" Piece "wn
- SM F Poukgo *an" Appltianae
Mch-Zehnder All Optical VPTEA VSTAar ,
Modulator
S"OWS"~~PEA SheN"u"iiChomm1110101 FN
Saa
ILU z
A*15
PIT~ Sr W@ * V N A
0 Poled Polymec Ilms
' I l citvn = Loeio 01661ionae 1oElsweetlcDevceAplication
* Flest Poiysmow Coaniel to Litu Hlobsio AePorteda Focus for Roeetach to Achieve Optinvum EleclroOptic
-4 Pstoel te Film Sudece
0 Nonfloeelse of 10-0 esu Larqp for Nontresonence butSO Hefdt to be Lager (- 0- "u few Broed Device
* Stage-ed-Al of 10-6 ev Wil Flind Aglctn InOpilca W.ve Guide Devices Such esOie iwtcliesmed Opically Conlrulled Memeusloe,
9 Thin Film Apgllllesn Such as Etalons Unlikety UnitesSlellcnI Advances Iln Largs NeetttineenltlesOtia
______________a."__4__11 _ Flae..and Optical CIty
~ Th. hs~ onma e Us a ... d
B-I
P. N. PrasadState University of New York at Buffalo
NONLINEAR OPTICAL EFFECTS
IN POLYMERIC FILMS
B-2
'~ LIS ' RC?5JY F iJC~~
C AEC'E
A.;AS 'I. 1-ASD AT -EPNSE 7-r- - AC AClu
CE~7~N CF'-Y LOW'CQ:LTCN7N
3ATE :NIVES" "F NEW y OR A T GGEL 3 UED "GE PROCE"3~-A~A~J~N7AE
SUFALC' NEW 'ORK '42 44 O~~CSRCLE
N OT E PiU1,RE~ D UiT ~A' YE D E SiA -R~A~'PRCCEBSING AND EV:C APD7ATNS
VI;p~ d'A I -,"ITAT(ON
" " IV C t ,t
0: c -* **
8-3
MI CROSCOPIC THEORYOF
OPTICAL NONLflEAITY
La- KITIO SUE-OVE-STATES .... Sait-fIPIR CAL,
ScF NCCmUCIEi PPP CODO INDO
DEPEENaC. 4NUMERICAL ANALYTICAL FREGUENCY IT-COL7UGATED
MEYMD METHOD DEPENDENT SYSTEMISI ItYPERPOLARIZA ILITIES
FNTZ COUPLED RESONANCt EFFECTS LONG
FIELD PEtHURED CHA IN
NETHOD NAURT -FOCE POLYMERS
METHOD
1C7STATIC HYPEXPOLARIZABILM~ES OF
DO PI1NG
03.1: ! Vf Relative =orunct -f . and0 , cor4T1rit~iunsCMISTR LCI CO 1 L.;TER :EpyV16&NIS
WITH A C401:! .0 L.S~s SZT:~.l o1 f .Arlo~us electron w%~.rves
.- electron conju~oatO efte.-I OPTI7.I THE 'TUntY StXl SCP
Sign of TCALCULTE 'IPCU !A- A FuC-oTO OF FIEL'
£fiIIatoO' of v tensor PcLTUcT.:C.. - GET
1ffe:? of suostitIt~ils
conformational tft~ DIFECi CrYESO
Effect Cf Structual it~onfortt Alt aef.CS ORIT.. OS"~TO TI ART
I1011tons. Dolaroft an lAUooIIWIaAlOapsTOtO1
lUNTOR FLO.ST 011011 FIEU .UCNU
iemify strictufal Parmters STATIC sECO1 %YPAtA ItTES (II
for CINIWKn its)
tlMRS'.-4T VALUE
MlITS OF TIS 1e"tO&CH;
?UVGR',7: -.1T-PROFNPUMS UiMl
L.E E-.JI% ExcaDSM
B-4SOME CONCLUSIONS CF ThEORE:CAL STUDIES F
"ICROSCCPIC SICNL .N4AR(TY
. THE CHO OF BASIS, PARTICULARLY THE RNCLUSON OF DIFFUSEPOLARIZATION FUNCTIONS. IS IMPOTANT IN DESCRISING TcHYPERPOLARZASLJTIES OF CONJLJATED SMA.L MOLECULES.
2. ' IS 'ANSOTROC. WITH THE COMONENT ALONG CHAIN
GROWING RAPOY FOR THE CONJUGATED HYDROCARBONS SERIESPOLYI INES. POLYYNES AND CUL LENES AS THE CHAIN LENGTH GROWS.
3.23. FOR POL.YNES, CHAIN LENGTH CEPENOENCE OF N IS FOUND.
5 5.3FREE ELECTRON MODEL AND HUCXEL MODEL PREDICT N AND NRESPECTIVELY
4. THE CORRESPONDING ORBITAL ANALYSIS SHOWS THAT THE SIGMA ANDr -ELECTRON CONTRIBUTIONS TO ARE OF OPOSITE SIGNS.
5. CONTOUR MAP OF TIR DERIVATIVE OF CHARGE DENSITY WITHRESPECT TO FIELD (REGIONAL CONTRTON ANALYSIS OF )CONDUCTED FOR POLYYNES. INDICATES THAT TE NONLNEARELECTRONIC DISTORTION IS A COOERATIVE EFFECT WITN ASUBSTANTIAL CHARGE TRANSFER ALONG THE ENTIRE .ENGTH OF -HECHAIN.
6. OUR SCF CALCULATION RESULTS FOR ( 'COMPARE WELL WITH THOSEOF TH SOS METHOD, BUT -( VALUES DO NOT AGREE.
7. IN THE SERIES RI - CC - R2. THE LONGITUINAL COMPONENT
-yZZZZ INCREASES AS mcE ELECTRON WITHDRAWS SROUPS AT l
OR R2 ARE SUBSTITUTED.
8. A COMPARISON OF y' FOR CIS'SUTADIENE , -RANS'9UTADIENE ANDTHIOPHENE REVEALS THE FOLLOWING ORDER
:
TRANS- UTAIENE) TI4OPN) CS- SUTADIENE
NIRP-ENE : : CnRSAE =;T jffl- :.-E I0E,:-
'r.,
BANE SAP/
3. loLI
f-l
I.. /
i $ * s
tC
B-5
Of AA .. WOW* 0' C~J'
R <=> &o !
3 ,5,- : , . -3 1
<a>
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cvC-
14-SC CALAT0mIsIl
MECHANISMS OF FOUR WAVE MIXING
I IELECTRONI C MOLECULAR CHARGE
CARRI ERS
RESONANT NON-RESONANT RESONANT NON-RESONANT !.10 2 sec
EXCITED STATE n-non 2 1 VIBRATIONAL ORIENTATIONAL SEMICONDUCTORS1PHOTOCOIDUCTORS
EXCITED STATE n2dx 1 CARSCSRS xDYNAMI CS
tlO-12sec - 1 2sec 1012 sec
10-12sec CONJUGATED LIQUID CRYSTALS,-ELECTRONLINEAR POLYMERS
THERAL
ULTRASONIC PHONON THERMALMODULAT ION GRATING
•1O'Dsec 10-6 sec
I
B*6
'S.' ~
b
a U
-- 0 0~ 0
i;~*- -~=
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~ = a Cc
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B-7 _ _ _ _
OESCAmr CAWE: Chajrge on Po I '0-*Saat.boe can biVariga .n aControlledwa-
RCSOC4ANT CAME: PhotoinaueeoS-Glitofl anmdBoPolarons createMOd Gap States
Re0:str~b)Jt,on ofOsCilator S renth~
Large XS tFast stesponse
11 OJO0-
A WW MID~qDO
ChBmcal @1. Electrochuobcal SwitchingOf etuaum High and La. States OE
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a
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3 -~i- S jVL -
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C-1
A. F. Garito
University of Pennsylvania
RECENT ADVANCES IN NONLINEAROPTICAL PROPERTIES OF ORGANIC
AND POLYMER SYSTEMS
C-2
RECENT ADVANCES IN NONLINEAR OPTICAL PROPERTIESOF ORGANIC AND POLYMER SYSTEMS
A. F. GaritoDepartment of Physics
University of PennsylvaniaPhiladelphia, PA 19104-6396
ELECTN .. F E STATES: MIMI OF TI4M 0 NONUNEAR
OPTIAL SUISCEPTIBIRl OF CONJUGATED UNAEAR CHAINS
C-3
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C-7
DC INDUCED SECOND HARMONIC GENERATION AND Yg
aw EWE, vo p
* SECOND ORDER CONTRIBUTION jz VANISHES BY SYMMETRY
VALUES (IN UNIT OF 10" 3 6 asu) AT 1.787"'!*
"2 |T)4EORY) - y. (EXPERIMENT)
BUTADIENE (1064) 3.6 3.45 t 0.2
HEXATRIENC (HOG) 13.9 11.3 ± 1.05
(60%t -40%1) (12.9)
S CALCULATED rg AGREES WITH EXPERIMENT BOTH FOR
THE MAGNITUDE AND SIGN
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C-17ELECTRON CORRELATED STATES: ORIGIN OF SECCND ORDER NONINEAR
OPTICAL SUSCEPTIBILITY OF CONJUGATED CYCLIC CHAINS
NMDVDA
z I • CH3
X (Mjm)
3.100 1.550 1.033 0.775500 1 1 I 1
400 NMDVDA
/ / / \ xp
V300 0.9f
7; 200 - o.oo ' "-- ,ZOO 290 320 360 440 00
WAVIELINGTH (am)
100/
0.4 0.8 1.2 1.6
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SYMMETRY C", (IV) (0) 12L*
3.92 3l1 -6.80i,3.78 00 -31
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400
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ENERGY Cmvl
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0. iov .ea) -27 t3 -19.7 -73.2
Ao N 0(1O am) -474 t52 -335 1 1347 1compmOin of ao£mprnw uhm SOCI.SCI Value of 0lpol MmmW
and the Soaord Order Mbueespis Suamepbly at 0.65eoV.
The percentage Comtbsalule of Diagonal Termi and OWf-deani Term
C-19
MPC
4
gNERtGy A3SYVMMETRY C, (tV) () (0
iS'3.69 4.7 -8.3 2.A" 3.69 0 -20.0
4W 3.54 0.4 -13.6 43AW 2.42 0,1 -14A1
eIt .92 12.0 -4.40
I A' -00~c 600 a0o
WAVELENGTH (nm)
600 ,p
300
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ENERGOY levI
M Ei erimeunai SOC) SCl;& ~&(ww" 17.4 ±2.5 21.4 I 25.1
ov (104 owli .123 t 22 -104.7 *238.4iLv 1 (IQ-" * .2140 :t 390 -2240 -5933
Cc Perim of 'Emp d Wi d ii. s SCCIValuss of 0Olpolo omand the Somd Order M.6easpiso Susamptt a 0.65 *V.
ISOCI I SC!55.5% 1 86.4%44.5% i 13.6%
Trh@ PsOPOWtq Cawbagimi of Otapai Term mid Off-dpnd Toem
C-20
DPHQ
4,
ENERGY 14~ &ALI 31-
(OV) (0) (0)
- 22
03A. 3.41 4.2 -86 .
is, 3 18 a -9.4 Z
ZA 154 14.4 -. ?0I-
WAVELENGTH (mm)
1 000 I
S-1000
-2000
00 02 04 06 a@ tO 12 14
ENERGY CiV)
OP40 SOCI' SCIp,(DO 25.4 30.5
$ .(10-" go) I-1410 I -626p.,6(10- em) -35800 '-19100
Compwisan of Expermu ertMw SOCI.SCI Valum of Olpoe MwOmamd "~ second Orde Miaosopio Suompstill of 0.65 ev.
I I SOCI I SC) I72% 85%28% 15%
The perc@m&C,~ Contuttn of Dtagoa Term and Oft-aagoi Tem
F-
C-21
ELECTRON DENSITY CORRELATION DIAGRAMS
( <An ef r (pn-pg)dr
r .OCNOI(SO-CI) Pf-Pg
,o/
IL- -- 4.1
MPC (SD-CI) Pi-Pg
DPHO (SD-CI) lg
-- 77D
-S
ii C
PICLED PCLYMIER GLASSES C-22
TIR SLM DEVICES
9%z %rap- o View
* (I-±iic trodesfl~fl I Iar' Si Chip
Orietatinal rderMNA SINGLE CRYSTAL
(2 . t) 1 4 8
CLAS SYSEM ±3,.di,(10Ogesu) r,,(1 0' 2mi1V)
CLAS SYSEM (l0.3OCms~esu1) (-1,9074±m) (X.633Lum)
M IG VNA 66 1 0. 0.3
RESCINANTFIGAOY 5300' 6 2.5
__________mNA SINGLE CRYSTAL - 1 230 67
LINEAR CHAIN NMDVDA _-- 2002. .MPC - 2100 24 - '0
CYCLIC CHAIN OCNOI 470 5.3 2.2OPHO 36000 410 170
*Measured at X-1 .58ITI AEREEN~1. Third harmonic generation study of orientational oroer innematic liquid crystals, Phys. Rev. AJA.. 5051 (1986).
2. Microscopic origin of second order nonlinear ootical properliesof organic structures, in Noninear Otr--l and Seiectrnattiva
eclIrnaLa (Plenum. New York. 1988).
3. Recent developments in microscopic descriptions of thenonlinear optical properties of organic and polymer structures, InProceedings SPIE = (1988).
4. Nonlinear optical properties of linear chains and electron,
correlation effects, Phys. Rev. B - Rar,- Communications (in pressl.
S. Symmetry controlled electron .crrelation mechanism for thirdorder nonlinear optical properties of conjugated knear chains, inFlotiroeenansivo Polymers Special Issue. Mol. Cryst. Liq. Cryst.(1988).
S. Nonlinear optical properties of polyenes: E!ectron correlationand chain conformation, in Nonlinear Onticai Pinartes of Polymers(Mate.4,als Research Society, Boston, 1988) I. p. 91.
D-1
S. Etemad
Bell Communications
CONJUGATED POLYMERSAND
NONLINEAR OPTICS
D-2
C c a-d le !C ,c *f~~~ ~ H C ~ C~
H m
H H H
t.7-
H H H H
r , rb r M rrc c Iw H
to T~3- i iJ
3 3 3 3 3 5 5
77777 W-N
D-3
Y"AANi06~Y
PEA *SARAA 1@4 n o)
l~QlY ~f6;Al 5A9
-A* 6 4A
D-4
(C)4)
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I A14
40w
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Ge __ . a .1w
Odo3 1"
D-5
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Il ,:3A ZI I I I
- -- I; 1. I; C
H H H H H
(bI 3w
4,,INOU
(C)
TWO~ 4444A*40tc A4.#piA)
FILA A -, 6 (Cc M
x (3 . (E, 4- w) (E, 2'p'. ,w (E1 ,
(E+ . 3 (E,- Z(E ., +
.. .... .............. .g 0 A , ,,, ,,, ....
D-6
\41 I ti
F H I -i
- X(J as
00 10 20 0~(DEGE)
IIRA ~ 7-3.0
SE- Irons~(~.
o -3
'o, hy ee'
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loo/, 1 ~4JtIIIA AJ e lA s
1 .2
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wcA c.5c A -c c
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20
10
00D 0,1
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200
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0990*Fgw ________ALA
2 - P&t&
64HAMS ijeAOSC6
((eV
AMPL E:
PICOSECZN fi
topT DE LSE
L1 DELAY
5 -51 ALM
f 9SOXCAft
0
15
20
5 *0
0 2
-1.02 0 102 2,03 3.04 10 2050 .A
P~PPRS DELAY (Ps) 0101
1. AFF7 0.75w- -
o 0.0 'a 0.5 1. 1.0l
DELAY (Psec,).5 1
0- eAk
--- -L - a 4s-
-" -6c 3C iOC 3CC
popPoo fw 0- .
5o-
- 01 2 3 102050PUMP.0ROSE:DELAY fPsec.)
tab%4 A&i44*4en?
(06% .Ace OtLh.4
D-12
*tOON4CAA . X ~~
OMM
af ? as 0* U LS 4.8 IL 1
fodw
I Or
I/ (
AIf - ,W4 PAWAnoft~ 'L"4~
I ~ %'A~rCAds
E-1
A. J. Heeger
University of California at Santa Barbara
ANISOTROPY OF THE THIRD ORDERNONLINEAR OPTICAL SUSCEPTIBILITY
IN CONJUGATED POLYMERS
E-2I,
-s. ..-r' 9
55
-,. ,.".,. ' -.
S
10
... .
2
gI
E-3
-44-
I. ,'- /.Y ,
IId
*1 -4
at
*~~4 c' uU
~t/, 4 x
I|E-4
-
I"I!i -
-I-|
t- 0 J I --
,V%/
S -
E-5
0~ ~ 0, -
0
-4.-
CC
~LO 0
(Aa ABO3NIUidojqfV'
E-6,.. c,, -'f'fI - -' - , .2 L j ' Pt~t - Y */~.I**..*
I-..' a -r Theory -. :,
$'*wo-'
V4t
""-"'"r----Y -1 - t I". . . , -- - ,. P , ... .
0.8 1.0 1.2 1,4 1. .
Photon Energy (eV)
TlIO A c
V j
..!,,,,,eW 4 .h.<,,. Vp;. .r .,,
! I"
I
III!
E-7
for..t ft-.y -- t- (
Dy~~~~~~~~.(.I ~~ ~ ~ ~ C IrC)?.g (.~S~,.3.)d. kj4._______
1=4. (Cfja~vh Ofd£ ~
C cc c, 41- C=C _ Ok
Tan -M (C H)
, ~i/300 K
J.V a)
I-v
-4 -3 -2 -t 0 I 2 3 4
(psi
W, ~4h O4SOLD
ho
0-
C- I
I ~ 4~W ML
E-9
01
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0.
~~~'.I.~~~~~ (Lattic Constants) OIC on " at -
.',S r, le ra * ifflt, :;.0 '
o /
U.0
o.* a.0 10t
s (Lattice Constants)
. . .. .,,a ."..
.Wae',.at.\
a t\e,,
,, ,, \ ,,
slatatemartat~a gota~I 0-ag -E~Ja..'~ C- -
-- 0 0a.N4.,%(L) amot \\
. .......... .. ... .t. W It 'tt mi ~ath I..i - - - - - - - - - - - - - - - - - -
IE-1O
3 ,\ f ~trans-C x ."
L YI
.1*, I t 1
hv (ev)
H '\I / \ /
cC c/ , / \ /
/ /
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\ C C /*. C/c %'
TRANSHFANHS
cis
13 ft-
E-11
.-
- -" ,--, - 4
I -- ' '. . . .. S - 5- .
,* . -- --.'----- 5-
i,* . 5
F-1
K. D. Singer
AT&T
NONLINEAR OPTICS INORDERED MOLECULAR SYSTEMS
1IIiI!
F-2
NONLINEAR OPTICS INORDERED MOLECULAR SYSTEMS
K.D. SINGER and M.G. KUZYKAT&T .2ogineering Research Center, Princeton, NJ
OUTLINE
R.B. COMIZZOLI
D.L. FISH @ NONLINEAR OPTICS IN MOLECULAR ENSEMBLES
W.R. HOLLAND 0 FILMS POLED UNDER UNIAXIAL STRESS
H.E. K(ATZ * NEW POLYMERS
- MATERIALSL.A. KING - CORONA POLING
- NONLINEAR OPTICAL PROPERTIESM.L. SCHILLING - MOLECULAR ORIENTATION DISTRIBUTION
.J.E. SOHN
MOLECULAR MATERIALS
*MACROSCOPIC POLARIZATION
pt)- x,0 l x8(:E,:+ .,2(t)E,(i)Ek(t)+ x ('~),t)ttt+
e MIC-9OSCOPIC POLARIZATION
*VAN DER WAALS MATERIALS
pt)- -~lt>
F-3
MATERIAL CLASSES
tifmwmaff Stwu L
~40autc Onefltatoehi Orce ww
MOLECULAR ORDER
o MOLECULES FIXED IN LATTICE
= N4 Z '~a~i(,)aJ(,)aiK(,) ... G L... (S)
*THERMODYNAMIC ENSEMBLE
EULER ANGLES x '.. V<AU >
2w w 2w
< ;JKL.. - > i =l f d cfsined 0f d'k;gL. ajjagjakg.r G(48b0 a
z
zw
y
F-4
SYMMETRY CLASSES DISTRIBUTION FUNCTIONG (0) - P(COW)
LEGENDRE POLYNOMIALS
'm up flO or pina poop '-
u u
448
ca mUownu for pow? grou-p.uIAs
42 42
(& xj~j1)'A 4J 18 U A5 'A 4L5 4A U la
ELECTRic FIELD POLING
SUSCEPTIBILITIES
*SECOND ORDER
X&3 - .B4P -l /3X- X4 - A* s. !< -l~3 5Lm.an ,alu IFM Wn, r~t
THIRD ORDER/
XiN33- .v .- - !-p,
15 7 35 1 add d
_ _ _m
/%gu
F-5
jPOLED MATERIALS POLING UNGER UNIAXIAL STRESS
/ * SECOND HARMONIC TENSOR PROPERTIES
*MOLECULAR DISTRIBUTION
exp-~(U~~m~E)1SECOND HARMONIC GENERATION
k- P 1(2) - 2d 31(-2w;w.aai)E (w)E 3 (w)
P?)(2w) -d 3 l(-2td;aWW) [I Iw - E2(~ dl 3 (-2w;w,w)Ej(w)
EXPERIMENTAL GEOMETRY SECOND HARMONIC INTENSITY
AM GLS*IMGAS A PPOLARIZED INCIDENT LIGHT
p(B)in(acoa 2 . - sil 29, )sin82. + 2acosS* SlnO, 00o0 2
I * S-POLARIZED INCIDENT LIGHT
p(8) -asin(9 2,)
zooc Zat
ORDERING ENERGY ORDERING ENERGY
exp(--]G,,(al) - 'T 2.
kT
ELECTRIC FIELD POLING
XB35I ±<P2 -L -7 35
kT 15 5 213
*UNIAXIAL STRESS
Up U- Us bP 2(cos8) - m'Ep,(coso) ---- POLfLIG
STRESS POTENTIAL DISTRIBUTION FUNCTION
[ (L, ( b) a( )P(cosoI +. b3-)3(0
(mT 7T(-)Ps(Coa 2 m*E a,
KJ <p> = 3kT A.,
,cp,> 3 a,cpJ 5 a,
ffogitule f ar oowmw<P 3 > 1- 3ab-siiasorng~ogqgj<pl> I +2a
2 1 <Pl> .1)
Ii <p> - 1 <P 3 >_U~Pt i.@ 3<P2>. '0
F-7
FILMS POLED UNDER STRESS
* DISPERSE RED I DYE DISSOLVED IN PMMA
Film Dye Numver Density Thickness Poling Field Stressv E4V.'c, f /cvw l ( ,?,dne/m2 ( Io 7 N
1 2.42 4,10 0.60 0.002 1 08 49 0.25 3.71
* RESULTS
Fil 0 .r- <,",> <p2> <p3> <P,> 1111
1 0.33 0.50 0.00 0.16 -0.020 0.00 0.015 0.0014
0 0.20 1.2 0.041 -0.20 -0.019 -002 -0.043
NEW MATERIALS
DISTRIBUTION FUNCTION
r 2 d x ,V 5 . E 7
* MOLECULES
*CORONA POLING
e POLYMERS
MOLECULES
OIL MEASURED BY EFISH
SISOTROPIC * DIRECT MEASUREMENT IN DIPOLAR c , ; LV ENT, DMSO
------- POLED
STRESS+~ POLED
@ INFINITE DILUTION TECHNIQUE
U
F-8
RESULTS
maimauis 00.
Dm1o
Dcv 280f
icy 4110'0
o j& in 10- 3 cmsD,...X . 1.350g*m* 5so-
CORONA POLING
F ~ -SUSTATS
" NO LEC1140DE DEPOSITON
" NIGMER POLING FIELD
F-9
RESTRICTED MOTION
- REDUCES POSSIBLE SUSCEPTIBILITY
- REDUCES DECAY MECHANISM
* CORONA POLING ALTERS MOLECULAR DISTRIBUTION
DISTRIBUTION FUNCTION
............. ISOTROPIC------- aY *CT'fODE P'OLM
CORONA POLED
SUMMARY
NONLINEAR OPTICS CAN REVEAL MOLECULAR
DISTRIBUTION
- INTERNAL AND EXTERNAL FORCES
* CORONA POLING
* NEW MATERIALS
I
F-10POLYMERS
SIDE-CHAIN POLYMERS
CH 3 ,H 3
1 r*
* HIGHER NUMBER DENSITY -
CooCH 3 CcOCH 2CH 2 -N*CH 2CH3
RESTRICTED MOTION
- EFFECT ON POLING- EFFECT ON RELAXATION LIFETIME
NN
ELECTRO-OPTIC MEASUREMENT
I 'I
--- ,.-.;;--o
F-11
ELECTRO.OPTIC MEASUREMENT
i4.
LA O W0 a
U! ,
w" ft (moo
RESULTS
MA1AIAL y d A,
O c Y V d m d A 2 9a d , -I_
I 13 I 3 I
(Owen)) d,. -I 1G"., IlaMA 1.52 dol.1
iMA
G-1
H. Nakanishi
Research Institutefor Polymers and Textiles, Japan
SEVERAL SERIES OF NOVELPOLYDIACETYLENES FOR NONLINEAR OPTICS
!G-21
Several Series of Novel Polydiacetylenes
for Nonliner Optics
by ..
achWiro MAKANIScI jR,
(Res.lnst.for Polymers & Textiles) A, eCI C
1. Significance of Crystal Engineering for F O
Aromatic Substituted Polydjacetylenes (APDA) R-C _
Z. APOAs by a tydrocen-bonding Effect d'C
3. APDAs by a Bending Effect (1) D R
4. APDAs by a Bending Effect(II) DA po(y-)A .C
S. APDAs by an Anchor-Void Effect S Y&A 0MIN4501al A. C I
B. APDAs by a Fluorine-Subsitution Effect
7. APDAs by Complex Effects -- X; Lit"
6. Preliminary Evaluation of X"' of APDAs o'(1. <4 <I.
FYIC.- 0. (ZhINrIo 10im * M9. Conclusion <3 <
V_."t :i: I M ( it
Coworkers II. Matsuda C. TAIteret atji. (J74)
S. Okada
N. Kato
S. Takaraci
M. Oht3uka
)Bandvidths(BV), Bandgaps(Eg), and Ionization Poten-
R R R tials(IP) for Acetylenic(A) and Butatrienic(B) Poly-
R diacetylenes By YEN Calculation.
R R R
D Substituents B Er IP
- in A 3.972 2.596 5.338
A (A) CR. in A I.AI8 1.769 4.903
CHi in A 3.265 2.449 5.039
R R R H in B 4.816 0.154 4.277
D "Z A CsHs in 3 1.878 0.215 4.133
R R R CH3 in B 4.136 0.435 4.032
Fig. 1 Interesting polydiacetylene
structures for NLO. (R:Ar) B.J.Orchard & S.K.Tripathy.Macrool..19,1884(1986).II
G-3
* z N z Z
~iie* ~ 1.
.F I I
G-4
00
- 0.M z 4
- - -- - - - - - t
._ -- -0" "-
-40C at a, I I I I . I Ia % 0 m tm n M13
4< C_ t " = ~: + .. - -
-. i -a 0 - 0,, o fo o• o ,
9, , 'C € , =
oo
9-., 9,,, '6
9, - * +
o . --,loin -.-."
oo
00
CC
'C3
~te,
CL c
- ~ + + + + I rt D
D (A r 9' 9'
0n2 9, rt
-.- 0
%-n -0oo -j -202~
0 * t- 0, o *- .. .J a I'i )
0* C 2
m~ -
w -, 00n C n w c
cr. 9~
- 0
C -4
'I*56 0
G-5
~o &'oo ~ Y'i .ow..
* S z . + +.
. .M a 0 IMPI" n Is 0
- --- 2r_+r +
n U - 7_ I 9 I
n Z
.< , -, ,0
- * 0 0
-4 C.,
++
'c CD oraie to curn (a >~.
++ +V -4V
* '1' _/ '
0 oO
Ln +
0 +V ,0-
o a
I .- +
Nomlsze horatcre n ( . .)
,~ *~ ~ ~ V.0-00 ~ . L~- ,. i- .0
OS
0" 0 C0
0 -4 v 4~ 0M. 0 ON 0C rr 0IN 0
rr 0l~0On - 0
001S. 0
U- 0
10 0U 0-. l~ M *0a
0 ~H S U-
0 0
ibebaa o3o
G-6
Z; ~ ~ a t
- C
1 . I I-
C 0 0
II 1+ E
S . m
00 000 04-
CA 0.
's -*A--Of l. s -
- a. "a•- i a _
rn o
-- - - C
O 0 O
000x000
I -* 000x00 '<- © I
.a a 0
4- z r=I' 0 0 0 ~ a0(
~~' Absorbance (a.u.,) I
0
0
:1 cii
'0 Zgo0
:27 0 )
CD a
0 -
3
003
Ct
G-8
I-. ABSORBANCE
I --
00
0 0
CI
NJ zJ
f- rr 4r* 0 C)
00N Jj
N
o 0 0
0 0
G-9
~~ m--- ~ ABSORBANCE
I-- > C>.*
C, 1 w Lii-
n 0t
C:0
+J co
0.- 01 N
II
010
n 0' 00
ril -4- 0
.1- 0- rr t m
1"-. 10:0 1 0
0 01
ft - -:r :3r r" 1-
0 o(1
ro D r
G-1
.9 ABSORBANCE
0 cr 0
0 0. r r_ 10
Pq M m M 0 4*n
0 0 <trt rt 0 I- IMa4H 0 0 0.* Ir I-':' m*
00 rn t rt rt 0
O~~~c: L - ~ - ~ 0
0.f4
o '
co 04 c 4
-I-I ~CAM MM X
cc . 0 0 . -
H-1
F. KajzarCEN Saclay, France
RESONANCE EFFECTSIN CUBIC HYPERPOLARISABILITIES
OF CONJUGATED POLYMERS
H-2
2'SC C :-.A:: -* !E' ~I..-2 32 - .nq ..r Oat
I..AA. . . .*.n.. ... n*.*... Ii A. .n.... .:.An.aI.*...I A3*4U-l l aCU....a .c 4. AMnltl u r41•DL ¢ml &a
L]t*S* " cetn~... n.
1. - 9 1, 1.4sy w e. 7 .. ... f&ile (0.00) A. .0 A fe i me f **f l.
T IN fILP PS~.II1?tO% n , LaUC3 ,/. . a . .?"1" 060911 OPTICAL ,T(UOPOLAUIS&ILIiT 0CK MM0INTI0. 2 ETIS.
-'nIO UCS i
E£lctri Fild t-ace Sao "Og M m c• GalaOtla-w
-f qOLVEAR SPCCTROSCOPI 1% PbA '-I- fILMS
&ftill-- .l a& nl .... .101 1. ....Telll-Q
a, a -r -i' 1l,31L.
.... I ...0 r .- , e . .i.
P t- t nteA, file ai, U.,t~e .. .....
f +0 l t ae [r ac ec rflte c s..
if . ... -. - ,)Q ..... ..
.- "... - ._
a - , 0, ,* ,oo ,*,,
., t/-- /
ijjl leftlmIl~aeatI2-Irn +llvie liue
3 - C..l V eee ili
Pllml~tilnl m i i~iI m . .1-.a Clel..
"- eee,'... ,,: . sest'. 7 .... . i.
It... ei 24T 4 ae..71
H-3
- C .. e - ... w . U i.. .......1EA.. -
- r...,.. No.. . .... 1 ..
T- AN it.. a. s* Pr. F.n, tnt .. f& .r oI... 1 t.. . q t ...
SOLUTION CASTING
WAVaJ1407 1901
-~~f Lo'; 1ft .. tt ... .,-t- ovel- of
tflft q-- - 1,"tt .. tt - or. t-F. Too* *
H-4
E,- .. ... I .... QC
IL4 03 ..6 0.7
.1a .- 844 . -.
.... .... t ...... ~a a .
frA. . ILI. ar f *.OC t."
F.. *LM. ~a2f 11n. t. ,At. ttA ft. 0
cx .t . UArqre of 0.7 te amfi.- 9
~*LWm~ ow maA~~flt@ow $AMU*00 ,.0 I 0 h.
230. AO 'St
H-5
POLYMER OPTICAL CENSJTY
I 0 -Q -l 2 -E
~ ~~~A ~POLYMERTHCNS ;m
X ~2~..W'e ..ae aeter Iination -LM
A am
'U,.: . U
U,..
uhm ~ ~ oh me 4 ffn0 WFWa
J. AWL 00S. '/6 S. IU Nw o I~3 "S
H-6 UCiENA
.... .... 'c ........
........ DcL.. .S-
- A
0Z 0.4 0. .
0. 0. 0.... 0.
~UNOAMENTAL WAVELENGTH (14mI l-
0.9 1, i.5 to8
jo.15 , .0.7
3 LU L2 U 1* III 3WAVE.D4GTI (WW
x0.3 0.4 0.5 . 08HARMONI WAVELENM~ 0.6-
IS 'LW. 1- 0.4--
.8 1.0 1.2 1.4 1.6 '.S Z..Wav.IontPLtr (Jmi
H-7"--'-
- 3
-M " .Poly - -3MqC blue form
1-4 A01
i U-t
2tj
1..
,- -. 1.2 1 .3 1.4 .
,Vavelenvqtm ?M)
I.. - Iu *rt 1~ I'.a .....L..L . Tensor elements contributinq :o 3j3oL x T(rom'm -)(,) E--,G
.... .sin , ce crt. te -3.... 'C '' - - - - .- - - ..
r ... ...
* , I-. - - - - - * .2 o . 5.
! 7 -"
'_ _ _ ..... A " .. . ""$, ",
*UlI _ _ _ _ _ _ _ Lm
awme. . . .rmamww tw hot~on rfe0n 4ance w ih
ooP03i te i o funcamoental )
symt1" level
.... one Pnoton resonance
* . -- ---. Io
H-8rensor tieements conrr nutiq :a ;DIJ -err ;..sceoti:)illt. 3
". -r e0-6
- ~ i 0 - - - -
'0-:r
r r r
N.F ___ ___ __ Re.'od .~ 95
-w phto-*-oan
'one photon resona'Inenit dependetindeofreractio
d'~ ' ________________
At ~ ~ ~ - -htnrsnac ooa
.rU.R.%
r..~00.T .)-s',s,
H-9
c -nn. e e C
a *rL~ LASc *inanc'...
en. **..m rens,
Lu -' lonneo Ce.,,..
. . . . . . . . . . . .... AE0 02*C t s o
0' 220
4,0
*: .,-,. j..0 ..
.. .",*stO . ?* 4 *. _a~ *,R..o le/t.
... 0. 7 - "-C-
plm m * Tm O6sJ
------ -- -----
¢lw l F M ' lt, en l I.t C l .- ~. C-.
H-10
-Ct,,. .. c. ..........
C ~ ~ ~ :' thi -O t.-.,- -IWt
Alsan U.S. 'S
,,-aa. Stf .... .aaf.
.a.c. -O.C ft .I
-* " - aett O'Gott.a .....
.[O'ER
I-I
Y. R. Shen
University of California at Berkeley
NONLINEAR OPTICAL MEASUREMENTSON LIQUID CRYSTALS
ANDQUASI-LIQUID CRYSTALS
1-2
n~t cAL- 7W pon
1-3
I~ L. L Ikk <6
7170- 72 n L
-L '.-02A~ ~ 2,I,, 4
V'a
1-4
.N0
0a.-J
0lyCs* ~
'I
5r 0
L.
V 0 0
0IC?-J -7-
dm-J (p 04
ii
SmaL2 rder~ --gli autp. jo mDWXuw - VI.
a a ~~~~~ (2m - i n 9 w 8 0 -
(106u)
gas : j
13 4a2
TV 79*
VI40 M 7S2
4AI4tzmbet _4,&U-L d-- CA
1-6
L.F. C.;
• . , . .. 4
1.20-C me.. % CHI mw..- c.,
- ..: * --.f- .
0.80
• . X.YA
.2 " -:" ' " *.' '
0.00
200 40: .- -600. Boo- -.Wavelen6gth 80Wavelength. nm
17(a) (bI
SHO (532 nm) THO (35f..6nm)
S-0 " . - omuky. Chi. nfbtw. 3SLabof.,
C Optical Properties..
.6w101
CU V
x0
Z Ir0000 U
N.NZ
%00
COC
E -77770 2. 'S L.
P% Ln
-uoidioqV nv'4!pq4dasnSjt~llu N<
1-9
Isi A
j
V V 0.
x0Iz
1.10T -I
SWIM W
______ 0>
sapmq' (g L
v v- 4-i~
-. 4 A A ~; 7- ~ >
J-1
D. J. Gerbi
3M Co.
NONLINEAR OPTICAL EFFECTSIN
CONJUGATED SYSTEMS
J-2
SECOND ORDER NONUiNEAR OPTiCAL EFFECTSIN CON.JUGTED SYSTEMiS a T. BOYD
DIANA GERBI 0. A. ENDER
R. M. HENRY
K. K. KAM
P. C. W. LEUNG
AMdANCED OPICAL. MATRALSSCIECE RSEACH LBORAORYJ. J, STOPKO
3M CORPORATE RESARCH LABORATRIE
ADVANCED OPTICAL MATERIALS PROGRAMOCRGANlC E3ASE:D OEICES)
/e!OCDEL=XG
SYNTIS CARSTW4, :ZA.T:ON
!3VELOPMEDI AND APPL:CATIONSI
" OENTIFY CANDIDATE MATEIALS X(2 ) __(3)
* UNDERSTAND AND MAINTAINOTCA MtNIAINV40LECULAR CODE
* DETERMINE APPIUCATIONS OF MATERIALS. IIIIII OPTICS LAS..W"11 01AFEASIILTY IN OEVICES TULcom omwn ToceNoLoamg
rum OPT=* LASOPIASESRRTCIN
A-
J-3
OUTLINE
L REVIEW OF SECOND ORDER NONLINEAR OPTICS, CHARACTERIZATIONMETHODS AND DEVICE CONFKGURATIONS
It ADVANTAGES OF ORGANIC NONLINEAR OPTICAL MATERIALS
I MATERIALS PROCESSINGIAPP.CATIONS
IV. ELECTRO-OPTIC MATERIALS - CRYSTALS ANDPOLED POLY tEfR SYSTEMS
MACROSCOPIC POLARIZATON: REvIEw oF SECOM ORDER uAIMME OPTICAL EFFECTS
~ ~ E+ L E.2I+I13! ELECTRO.OpflC EFFECT:2 r= uP,-~r Em
hnftx of refractUon changes with applied voltage
n = n. +A&n(Ea n x (
2 1
SUM rEQUENy GENERA1nll
Output frequency = sum *I Input frequencies
wfOut) = w, + W,Sl4OR 142%vld,([X121]2[1111-1] 2MICROSCOPIC POLARIZATION:
DIFFERENCE FREQUENCY GENEDATIONS
Output reqpmmcy = dilference O Input frequencies
p =p *~E A E Eh4 (jtEtEkEA IoGut) s~.
c2 ARAC TA1,O hE'N0OS
R
SECOND OC NOLINM OPTICA. MAT84ALS
SltI5 cKMWL. Ste
*zET~-om Ww
J-4
] S FI. E 00 2
1(2w)sample1(2w)urea
ATEIAL FOFM FIROCRY E OWDER MATERIAL FOFM SOLUTION (LOW POLARITY SOLVENTS)AAFANTAGES OBTAIN MOLECL.AR PROPETES.DISADVANTA GS CANNOT RESOLVE MIRO ANDCO P RS N
MACROS IC CONTRlIPONSARTO NCONLEARITY DISADVANTAGES. MOLECULAR PROPERTES ARE
SUBJECT TO ENRCNMIa4T
F - E \ P
MAKLER FRNGE FR H
20w. 2. Exp -mm~mW f. Ums "- SEC mmw ,mm - ,,-Lm~ wwF..wm pwy a1n P. P~q .0 V, hom L. S200F, Gk-p CT. w M me dm D.
20 0 20 40
I ANGLE
MATERIAL FOt LARGE SrIGLE CRYSTAL (rnMn to cn)
I ADVANTA M.aj TENSOR 5----2P MATERIAL FORM: POLYWER SYSTEMDISADVANTAGES, IES CRYSTAL ORINTAON. AADV4ANTACES: REAL LF ElNFO9NMENT.
S OF REFRACTION POUSG EASY SIGNAL DISCAMIATION
DISADVANTAGE NOT A DIRECT mEASL.O4T FOR E-O
I
J-5
CmOP EFCrI
A- ADVANTAGES OF ORGANIC MATERIALS
[ SYNTHETIC TALORASLrTY VIADEOA TIONWSBSTIrhETS
77 ---- k SI.SP!COSECONC RESPONSE TWES
TRANSPARENCY
rip". I, MECHANICAL AND STRUCTURAL STABIJTYA. m hii... n s C.
HIGH RADIATION DAMAGE THRESHOLD
ENVRONMETAL STABILITY
SPROCESSABIJTYMATERAL FORM PO.YER SYSTEMS, CRYSTALS PCOc T OPEATflc OF DEViCS
ADVANTAS DIRECT NFEAS (DEVKCE FO
OSADVANTAGES. LESS SENTlVE THAN SHG
NOT AN N-SITU TEST
CRYSTALOAPHIC ORIENTATIONFOR CRYSTALS MATERIALS PROCESSING
2110964nWE POL.YWOMS
e-g. CHANNEL WAVEG'XES,
SREOL ESLOW LOSS (<1 sB/cm)* R r i F WELL.KNOWN
TECHN)O.ES AVAILABLE
I DUCE OD RATHER THAN RELY
ON CRYSTAL PACNG
e.. BULK CRYSTALSCHANNEL WAVEGUIESVAPOR DEPOSM FILMS
* REO.IRES LOW LOSS (<1 clB/crf)
SBULK CRYSTALS MUST BE DURABLE ENOU"4FOR CUTTING AN POLISHING
SCO PLETE CRYSTALLOGRAPHIC ORIENTATIO,IS REMUIED
-PRNCPL OPTIC INDC AND AXES RELATIVETO EXTERNAL MORPHOLOGY 4&ST BE0ETERM
J-6
SECOND HARMONIC GENERAT'ON APPUCATIONS
rd w bue 2W
laser die", S waegfuide
doublig optical frequency gives 4x storage density
APPLICATIONS - ELECTRO-OPTIC EFFECT
"wduW4t directional couple
G/*. ..
• -I --"-_,.
1
J-7
ELECTRO-OP7T:C PHASE SH:'FTER
,'OOULm'TOR, GYRO
*COMPAPE -'Xu. ELECTRO-OP71C PHASE SHIFTER
\fle d
cN/s E =4 Wflw
J-8
RELATIVEHALOfNITROANLW'1ES EFFICIENCY u DEDVE
(URFA)i
02 N~,20 4.471
~2
-'ar
Ca _ -
2 7.722
0.02 3.23
acl
MAUEIL s~cg ab W2
S-chIers.- I Int1a P11421 30.844 I3.952 3 6.004 3 90e goo9 4
(phast 11
*., m~tuteall. 7 .344 7.844 1.091 97.96 116.69 SS.23 2
(9-chlers-2-altresalimeI.)
3-chlers-4-aftreaamillm P?1 /C 3.813 12.S31 14.467 96 91.20 to 4
*A. T. McPhil and G. A. $11s. J1. Chow. S. * 227 (196S)
J-9
WIMECULA R NX)ELIING
H*O WUMO
14 IIO1-4 H
S,4 diffee e in grixinI' stlate a..i( excitedst e
difx i rmo"ent s
5-CHLORO- 2-NITROANLINE ca
a 30.844 A SPACE GROULP
b = 3852 Pna21c = 6,004
CA
B
Figure 4.. An illustrazon of tihe crystal structure off 5-hor2-nitroilne Signfian;ntr -and intermoleculaur hydrogme bonding indicsed by thins lisnm.
" II I I I I I mil
J-10
5-CHLORO-2-NITROANILINE
SPACE GROUP Pna2,
polarization axis : C-axis
P X(333) /(zzz)COS 38
.1Z
-~ C
polarization axis of moleculeCi i polarization of crystal
C
Fiqure 5. A projection oi the nbbon-like packing structure of 5-chloro-2-troasline. Z C = cOS 0 =0.906Molecules in each row are connected by siagncant ine emolecuLa hydrogen bonding. P0
SHG PACKING EFFICIENCY 0.74
2-CHLORO-4-NITROANILINE
ELECTRODE CONFIGURATIONFOR MEASURING E-O EFFECT
FIGURE OF MERIT :1 nV'r.:-nr::l= 18 pm/v0C.
E = y
J."'
SHG STUDIES OF POLED POLYMERS
EFISH on 3-CHLORO-4-NITROANILINEPRINIPLE OF POLING GUIEST/HOST SYSTEMS
E 0
1.0 lncroni ______ 0.532 FTUi 04
INVESTIGATE:
0 Extent ot oroerwig
* 1h-situ
* Po" goyriaryics
- CUALLA? AGREES IEMT fASMRD
Z. l2co I X 0l
E. RT! X S 1
z ~. 6 X1O V/cm O 30 e)R. X 10-10
-r - 1100 3 - 0 '65 hr). ft? 0.3 X 01
J-12
POLED POLYMER SYSTEMS FOR ELECTRO-OPTIC EFFECT
448 IX d2%-.Ww)~ A/15a0.GUE at t" ndcrns BIGhm n1000 in 1300 nm I0nOh
3MX-40 37 84 51 30 27
3MX-3 19 1.5 0.13 0.09 0.1
3MX-36 18 0.6 0.3 0.3 0.3
3MX-2 15 0.5 0.6 0.6 0.6
3MX-1 11 0.07 0.06 0.05 0.07
3MX-8 10 0.03 0.04 0.04 0.04
K-1
G. R. MeredithE. I. Dupont DeNemours and Co.
OPTICAL NONLINEARITY: MOLECULES,ASSEMBLIES AND WAVE PHENOMENA
! L-1
I G. KhanarianHoechst-Celanese
CHARACTERIZATION OF POLYMERIC
NONLINEAR OPTICAL MATERIALS
L-2
Thiarac~:r=On -t 'ioniirear:H
-oticai Zganic .lteris EATN
D .-4AAS
- .ESUE
-4 MAN-<hagianaui
.~STAMATOF;W
iqoecnat :~tneg Carooratioii3 !NG
Summit. Ndew arsov )7901-4 YCCN
ACS Norxsnroo
Virginia Seacri. May. .988
LJTh-INESchematic0 Moiecular Miller S Rume
Design of (intuition, computer modelingorganic molecules anid quantum mechanics)I
0 Doivmer Strumure ariaSynthesis
I (Optical, efectro-ooticaL.)Char actei ization (Solvato-chromism i
Materials i (Str'uctue/ propertty algorithm)o Measurement of D v Second Harmonic Formulation of (Guest-liosi single
Gener'ation Development polymeric systems TrcmonntLc
0 Masreen o o th PcktsEfemFabrication (Thin films, 3D articles)
Fabrication to (Dimensions & relation to0 Rauit fr NAPIMAcritical standards activity, shape, size..-)
anvceDesg Conversion t io device forinal0 MNAJPMMA/SoI-G9I Glasses - Role of Motlculi n
Motion Evaluation Evaluation of device
o Larigmuir Blodgett Films - Rote of InternalOptical Field
3 Aooiiucation to Oevices
L-3-ANHAFIMONIC 3SC:LLTOp MODEL
BASIC PHYSICS
M mug ot ectan
MOLECULAR0 Ww"vg of eci.
N oasllator Sttrgt
P E Zu +, -- E, , F'- w.+ ~ E +E anhermofic cofisafit
L
MATERIALSanguear tiu"Cy
L gm of mof0AS
P " - "E + X'"E' - x E
ExO. ria"*Gul *Sl
N , 3.0
log.43. versus log.a.
Verification Of molecular Miller's Rule
•,. * 5-4t' /E/
7,,
+"
o-.-
/
,S04
i6
I
L-4
- , .. : M¢IAULL I
.- , .. M l i ma Kerr Col i 1 It s K ( I 0 9 U) l n er PO 'lM IIag4 IIIV * , s 1 0 I J U
St ' Un *,1A nd I 0 esul
111.lcomin -9
(.11 -.0.0 @ ot P403 09 5 j2 0
It- _ O<al 6850 isn 5
- - -11,4~ -~~I0 145 295 20
TN,16.9 J96 1a
-Is -9000 -.. .tv
.9 bahINS ati 0611 Pat q Is been deudl3Cor"1 equadls"t J. And
* ~ ..oZn vtbt Sia.)I 111atur. .k*s for the dipole ma I 0, And the Averbqe pol'.1,latliY.
S at90rt.00?., vdflat eftetd Abe W5* A Ic 9p. A OlSiltrSIOn fGFRIMI, h" b~tl u%Cd
to9 gorom 0bii t 191 Pro It. A* Also. 1 1 91 pmw* •aI . St vf role *ll
O F POLED FLEXIBLE 0IPOLAR POLYMERS
Types of Molecular Packing
Packing Type Order Magnitude
\/ Non-centric Second Moderate is Theory swise as f-r .roh
Non-centric Second Strong
r"$ d Centric Third Strong
Centric Third Weak
-t=; -l +tt
+ xc Wg0 JSOI be dhO for OO f cr3lfS FlOryDirection of dipole moment
L*5
H '
>0 CSH4X H
/ 1Ta 2: Aveaqg moflhI Sumomatbifts for
H ~Vancus mommawu WO.0t6 C0004vimmu.
FIG. :. otauua ai Walls of PeNS. X -NOi.
Wr. , MnmrUS.n (-l. a0.Momcuar iCad NUR,.W of %1, St /A Emmancemern
TABLE U. u)z(1 i) a(U/(- 10-" Se' M- c polyo-o*uvaemst6. vs NLO OcnoaIorwe 51tacicy p, r -Z9g K. x - 200 -.~ uOa. '7.000 37 &30 is
P, (0Z0 70.000 152 1140 20
1. 0 (timcace) 23. 5 10.7 9 Omeffened Dy GPC remom to o"yWww,0.2 16.6 8.27?
0.4 16.3 6. 12 0 Stfua tu01 ImY TODAb10.6 16. 6.360.8 11.4 8.17
0 (svadlomauai 1.. 8 .23
c. S. W-114m. S. F- Fern. M. Sozrvu. ainc 0. J. Wimary
COMOna. A6Sawe?' LADOrmon. EaSmman IKoaa
~ AY "S . a6: -Carmoany. Rocnewpr. p. y'.
Mulvaney
C. S. Marwi Laleruan..0oanvmor totCftarmany,
L~n"OrSITy of Anzons. uman AZ.
Maker Fringe of EFISH of Dioxane
Laserx 2]Geneatorat A-1.535um HV= 5.0kv
L F 13 VA**" I
SiearpleCO CAMAC Crate I
LC -c L1, I I c
Lc II'
Am
L-6
Second Harmonic IntensityFrom a Poled MNA/PMMVA Alloy
E
M
U
75 . 5
0 F-N AMNCGNRT1O RMPLDPLMR
Roainai
-h0 eodnroi tnivmgvnb
1( .
S 7CONO iAcOI -(E-AT1ON RO ...S ."MYMaR
d Second harmonic coefficienit
Popeifo fl C1 of d tentor onto optcal elctric
1, Coherence length
n Refractive index
I hcw a ati Polarized incident
e Angie of .tSWo laser beam
x (-2 .0 2d
When 0 - 0 p - 0 and re ia no comoonent of d a*ang E, andtm. ol MOa Second harmonic Oflaetved
The M&Wa finge arms fronm an mfteternice beteenh theI unda~Wa beam am1 generated harmonic wav.
L-7
-E,=v :a 'AEASUREXM4E% POP 0CXZLS AND K(ERR EF-EC- CKI- 'F
The ooticai retardationl s
The asretnnrganCe an induced in a Koff coll it: 2v I an
.%n - ),BE'
I Optica path lengthand n a Pocxi codl:
,n 12 r EAn Induced birafnnggflce,
Wavelength of light
-he wirefringence results in a retarationl rThe induced birefringefica
-- 20ant
4nl - I In: r, n: f,,) E
in the small angle appfaxiinatofi. Equation 4 becomnee:
(I . r1 r Pockets constant
n Refractive index
A SiMUs~dal voltage is aopleow actass the siscm)-atic cell E Appiod @Jelec ield
V . Va awt*For poled matenils
Suostituting Equation into Eauatpon 5
-- :wf Pociei Sinwt rKerr ca2v 3
This result is obtained iram a wernoidnarnic moeal for poling
Boltzmann statisnlcs
The aaaawant aingular deaendance of the Pockets effect aises; fromctmange 0f octicai Dath iengtri
wow a is C th thickness of the sandwPoeOley r
The analyzng light beam sees a differft bireiringence aJunction of an"/4
- -- Poiarized
&n (et - &n ie -90) sine* Laser Beam
eis the angle between the nrmala ofl a samofes and tihe lightae~m
L-8
SCHEMATIC OF ELECTROOPTIC APPARATUSGUAN lEA
WAVEPOLARIZER PLAIE ANALYZER
IV SUPPLY U
SIGNAL IlEFEFIENCE SIGNALGE NE HA 7On
Pockels Effect from PoledMNA/PMMA Sample
(Angular dependtfICe)
InteiisityIaib. uruts)w
0.(r 10* 20* 30* 40* 50,Rotation angle
Pockels Linear Electro-optic EffectFrom a X("1 Polymer
IntensityIart). UJIIIS)
0.0 2.7Electrical held (V,,,/pamt
IL-9
"OL-GEL rECINOLOGY
i
POLII1fllC - CBOSS-LINKZD POLYNIZS/
LONG-CHAINED IOLECULIS
COLLOIDAL - LIIKED COLLOIDAL
PARTICLES (SOL
KERR EFFECT OF SOL-GEL GLASS
MNA added to sol-gel glass
PMMA is added to sol gel glass to give mechanicalstrength
Slab was cut and polished for electro-optic measurement
Arrhenius Plot of Kerr Constantfor MNA Optical Composites
1.5
1 13 0 00E
0.5
0
Log -0.5 00f1(TI/(2981K
-1 5Zw/w MNA in PMMA-1.5
0 5%w/w MNA in glass/PMMA a.
-2
-2.5
-32.5 2.8 2.7 2.8 2.9 3 3.1 3.2 3.3 3.4 3.5
103
1/temperature (K)
:, !
L-1O
THERMODYNAMIC MODEL
NLO Side Chain PolymersFirst Generation
Assume that nonlinear ootical molecues are distnbuted CHI Bonentationally according to Boltzmann statistics. _CHZ - ab
C=O
, Nr. iA - 2) uE o
n- 2, 5kT (CH2)n Spacer03IoL
N numoer density NLO/mesogen
f internal field 0hyperpolanzability NO n-2,3,5,6,8,1 1,12
,U diDole moment
E poling field
k Boltzmann constant
7 temoerature
t dielectric constant
n refractive )noex Dependence of Glass and Clearing Temperatureson Carbon Spacer Length
RESULTS Ion-90 --
70- iiKSam ple _ ' -2...l _ (-t, ..0_ _ "(calc... -2 fo - -- N .: ,,, ;" " .
~5ON S'E410% 4o0--
MNAJPMMA 1.6 1.5 0.6 - - -
t0 - T-
I 2 3 4 5 6 7 8 9 10 11 12 13 14
Number of Spacer Carbons
All '" values are x10" esu and are at 1.06 /um
- .. measured at 1.06 vrm
x-,(-....0) measured at 0.63 urm and a dispersion relationwas used to obtain values at 1.06 urm
I(Calc) used the thermodynamic model
L-11
NLO Polymer PropertiesL..;',,VU.JIr SLCDGE , FILMS
x 12) at 1.3 pm >50 pm/V
r (calculated) > 14 pm/V
n ( 13 pm 1 1.57
e (DC) 3.5 C .rna,,.i o -o.cwa by Suraam
e (n2) 2.6• .Y~SIW Of aCRtIIC T SIudh..s 0?
waveguide loss at 1.3 pm 0.9 dB/cmSpin coatable from common solvents A wscon o . auo .1n mo..c(,es
Poled for applicationStable (<to% loss? at >50"C fot 5 years
Langmuir-Blodgett Film (LBF) Formation
" Is tnle deposition on a surface of a single molecular layer at ahignly ordered state
" Sequential deposition leads to periodically structured films - '01, oot., ...eine ha *He=
" It is done by transter of a compressed molecular surface layeron a liquid onto a solid surface by dipping
Transferred layer on solid surface
Molecular surface layer
" Applications
- Nonlinear optics: Bistable switchesThin film SH and TH generation =3o-
- Electro-optics: Thin film light modulalor 1' /
- Integrated optics: Planar dielectric wave guides
4 XI 4i
.: , . ;i . :0
5, ACTNN. AREA JASB TIC M
g. 5. Plot. o( the 5emod-honC (SH) signs 7 v-0 wa
1 x i relative to the quartz teference slab versus the area iracu t
--Jied by the dye in the aIted otooisy.
.0. ,;u' tl - t* I. ItS. O.. . P 010
L-12
-::a!. :=t:cal Electri~c -eld -:near Aear rx~:Z
* .eg.,ec: i'jct;at-on :n :::e
* - *z; F, A YF , 'yzzz) F . moment
* AssLme :Mat !:near oo:ar::3ol:ty
i alone zhanges 'ocal aynam::
2 3 1 2-or
S ana - are tne d-.ooe moments a
3n:o =olarz:aoil.t:es
p - surface density of ::=Oes
Z 3x:s :s normal to glass surface a -aoius of non2:near ot:c:::nolecu e
=esuits for tme nonlinear
susecotjnl1ity
Variation of effective X... of a Langmuir BlodgettFilm versus normalized concentration of active
,.... __ 3a 3,a x nonlinear otical molecule
2 of__ z z x ) 2 2 , c zz I * x z
- L
a I
U
S_
L-13
CL.ASSES OF ORGANIC 14LO DEVICES
IElectro-Oic Devices. POLYMER GUIDE FABRICATION PROCESs
COMPONENTS
- Control of light with electronai
Appolications: Hybrid optical processing and optca Spin Coating (thin film formation)
communicatios -Buffer Layer and Substrate Materials
0 All Coticai Devices -Patterning
*Metallizing
- Z zn ro of lig ht w ith lig ht
B e a m C o u p lin g
- Aopicawions: AVl optical computing and ultri-laitoptical communications
ouloutsignal
Eiectrooe
4 floul
'aser beam S) Secona ciaacinc:aver .4
Anaiyze,
Suostraie1,11- active film -rsi ciaacufic
Eiec~roae aver
-, iarizatjor.
M -)oanzalion
L-14
MODULATOR RESULTS
MATERIAL LENGTH; Vw A F r3
(CM. (V (nm) (MHz) (pm/V)
PMMA:pNA .0 450 533 30 .5
!HCC #0520 1.0 45 633 0.5 35.
'HCC #1522 2.0 30 830 10" 3.75
HCC #1238 1.5 4.0 830 1 20I
3 A G
r - 2nXLV,r
r .85 to .95 for these structures
T-HER MATE__-A- RRORERT- E
; P 0- M~ -. - -g " .
" "- H _ "- -
SUMMARY
- Organic NLO research at HCC has developedoutstanding NLO and EO polymers
- These materials, additionally, exhibitcombination of excellent performancecharacteristics and fabrication propertiesfor NLO and EO devices
. Initiative to develop a series of importantNLO devices has been undertaken at HCC
- Fabrication science and technology for thematerials is a key component of the initiative
M-1
T. Richardson
University of Oxford, U. K.
PREPARATION AND CHARACTERIZATIONOF
ORGANO-TRANSITION METAL
LANGMUIR-BLODGETT FILMS
1
I~II
pI
MAN2'4 NfP&IArTIO AND 'q4AEACTERISATI2M 'FI
'gA~-rp 6! E VAL 44fiHIR-AfL~nF- -'q Vs Hit
T. RICHiMIROO..jONETS
PARKS No"B. "ION OnPJ. VLW
A E.C J0YVKA. S.6. DAVIES ';-0
SOOTH PE % IN AAOIES
SUHPARKS MAD. 00,01. 0U1 WI. EUWLAI
A SEES OF NOVEL RUTHENIAN CU~ HAVE BEEN DEVELOPED FOR 005 CCVITO THE LAIIR-gIO0NET DIPOSITIOW TECIQE. CONPEI46 OF A£ .P,
A- RUTIHENIUM (CTCLIIPNTASIENYL-SIS TEIPRENT.PHOSMINEII NEAR
GRIMP TO A CYMOTEAPIIEIL LIQUID CRYSTAL MOLECULE WAS ENR SHOWNI7 R uTO ICREASE THRE SECONS-ONOEH WOo-LINEAR OPTICAL
NYMPOHLANIZASILIT 011 FURTEMOE INNCE POTILAVER FOMATION.
OPTICAL ABSORPTION DATA NAVE REVEALED THE EXCELLENT Ph2 P PPh3IfflODUCISILITT OF WtCESSIVE HOLATIS TRANSFER. SECONDI
HARMONIC GENERATION HAS ENR OBSERED OI THE EFFECT HAS ENI( (b)INCREASED IT INCORPORATING OBUOSTITUTSO LIQUID CRYSTAL MOLECULES
INTO IKE V"IDS BETWEEN TIRE TEIPHEHYL CHAINS OF LOJACAH OTHENIU
SUBSTITUTED MOLECUILES. WE HAVE FRITNER OPTINISEO THE 101-LIKEU FIGURERESPONSE BY SYSTENAT(CALLv VARYING THE ELECTION-IELEASING
CHEMICAL GROUP AND THE CflNJAATION WITHIN THE MOL.ECULE. Ai A TYPICAL CTHIOTEPNEVI ROLECULE M .
(5) THE 1ICsHrI to PN 1I7 I SORSTITUTED NOLLCULEPOSSESSES A LAIGER SECONR-ORDER WON-LINREAROPTICAL HYPERPOLRIIAIILITT TOM CONPOUND
25- 0.06
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TOPICS
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" GROWTH OF THIN SINGLE CRYSTAL FILMS
* FABRICATION OF DEVICE STRUCTURES
" DEMONSTRATION OF CHANNEL WAVEGUIDING
" INTENSITY DEPENDENT PHASE-MODULATION
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" THERMAL STABILITY (THERMOCHAOMISM)
" SOLUBILITY
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CONCLUSIONS FROM NMR STUDIES
" THE CONJUGATION LENGTH IS DETERMINED BY THE EXTENT OFPLANARITY OF THE CHAIN-BACKBONE.
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" THE ACETYLENIC FORM IS PREDOMINANT IN POLYDIACETYLENES
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* IN THE L-8 TECHNIOUE A LIQUD IS USED AS THE SUBSTRATE.AIR IN THE SHEAR METHOD SOLID SUBSTRATES ARE UTILIZED.
INTERFACIA THE L-8 METHOD APPLIES TO AMPHIPHILIC MOLECULES ONLY.INTERFACIAL .THE SHEAR METHOD IS APPLICABLE TO A BROADERREGION !RANGE OF MOLECULES.
* THE L-B METHOD PROVIDES ORDER ALONG ONE DIRECTION ONLY.THE SHEAR METHOD LEADS TO 3-0 ORGANIZATION.
WATER 0 THE L-S FILMS HAVE MICRO-DOMAIN MORPHOLOGY (POOROPTICAL QUALITY).THE SHEAR-GROWN FILMS ARE UNIFORM SINGLE CRYSTALS(EXCELLENT OPTICAL QUALITY).
INTENSITY DEPENDENT PHASE MODULATION
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FOR O.8 TO 2.0* (HERMANN ANDn2 OF PTS- 7 x 10
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2/MW SMITH. 1980)
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SUMMARY
" A COMPARATIVE EVALUATION IS MADE FOR DIFFERENTPOLYDIACETYLENES IN RELATION TO NLO DEVICEAPPLICATIONS.
" C'3 - NMR RESULTS SHOW THAT THE CONJUGATION LENGTH ISDETERMINED BY THE EXTENT OF PLANARITY OF THE CHAINBACKBONE AND NOT BY THE CHAIN LENGTH.
" THE ORIENTATIONAL PRINCIPLES OF THE SHEAR METHOD AREDISCUSSED IN COMPARISON WITH THE L-8 TECHNIQUE.
SUMMARY (Cont.)
" THE SUPERIORITY OF THE SHEAR METHOD IN PROVIDINri GOODOPTICAL QUALITY SINGLE CRYSTAL FILMS OF CONTROLLEDTHICKNESS AND ORIENTATION IS DEMONSTRATED WITH MANYEXAMPLES.
" CHANNEL WAVEGUIDING IS DEMONSTRATED (PROPAGATION> 5 rmm) FOR SHEAR-GROWN PTS FILMS.
" PRELIMINARY RESULTS OF INTENSITY DEPENDENT PHASE CHANGEIN PTS WAVEGUIDES ARE DISCUSSED.
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Universitat Bayreuth, West Germany
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POSTER SESSIONABSTRACTS
Optical Kerr Measurements on some Ferrocene Derivatives.
C.S.Winter. J.D.Rush and S.N.Oliver.
British Telecom Research Labs.,Martlesham Heath,Ijswich IP5 7RE,
ngland.
We report here preliminary results from a study of the third order non-linearities ina range of organo-metallic compounds. These initial measurements have beencarried out carried using the optical power limiter technique developed by Soileauet al 1), where the critical power for self-focusing is measured and used to calculaten. The materials measured were solutions of ferrocene in ethanol, varying from101 to 10"' molecules/cc and a liquid ferrocene derivative,bis(trimethylsilyl)ferrocene. A value of Y for ferrocene of 4.1x10-1 esu was foundfor the solution studies, in good agreement with that measured for the liquidderivative of 4.6x 1073' esu. The experiments were carried out at 1.06 am with 10 nspulses. We are currently repeating the measurements using other techniques andshorter pulses to distinguish the various possible contributions to the observed n:.
(1) M.J.Soileau, W.E.Williams and E.W.Van Stryland:IEEE J Quant Elect..OE-19,(1983),731.
Theoretical models for the second hyperpolarizabilitv ofnovel conjugated polymers
David N. BeratanJet Propulsion Laboratory
California Institute of TechnologyPasadena, CA 91109
Theoretical models will be presented for the chain length dependence of thesecond electronic hyperpolarizability of simple polyenes, simple polyynes,and more complicated unsaturated organic materials. Thehyperpolarizability of conjugated polymers which incorporate novellocalized electronic states will be described as well. These material, presentthe possibility of achieving enhanced hyperpolarizabilities due to mixing ofappropriate "gap states" with the delocalized states of the conjugatedpolymer. They also present the possibility of designing materials withswitchable" hyperpolarizabilities.
NONLINEAR OPTICAL PROPERTIES OF TRANSITION METAL POLY-YNEE
E.A. Chauchard, M.P. Cockerham, P.L. Porter, S. Guha, C.C. Frazier
Martin Marietta Laboratories
1450 South Rolling Road
(301) 247-0700
Data from third harmonic generation (with a 1.06-um fundamental),
power limiting and four-wave mixing measurements of solutions and films of
transition metal poly-ynes were used to verify that these compounds have
large third-order optical susceptibilities. The large third-order
nonlinearities observed in four-wave mixing studies of metal poly-yne
solutions may originate, in part, from contributions from the real and
imaginary components of intense two-photon absorptions associated with the
metal-organic compounds. We will discuss our latest four wave mixing
experiments and the direct observation of two-photon absorption in metal
Do.y-vnes.
We will also discuss the correlation of polymer chain length and
structure with third-order hyperpolarizability per repeat unit for several
metal polymers and oligomers.
REVERSE SATURABLE ABSORBERS: INDANTHRONE AND ITS DERIVATIVES
R. S. Potember, R. C. Hoffman, and K. A. StetyickJohns Hopkins University Applied Physics Laboratory
Johns Hopkins RoadLaurel, MD 20707-6099
Indanthrone has been shown to exhibit the phenomenon of reverse saturableabsorption. 1 The wavelengths at which indanthrone behaves in this fashion canbe changed by structural modification of the indanthrone chromophore. Thederivatives which have been synthesized have been shown to be more efficientreverse saturable absorbers than the parent chromophore.
It is advantageous to extend the range of nonlinear behavior to any desiredportion of the spectrum, and this is best accomplished by substitution on thearomatic portion of the indanthrone molecule. We have demonstrated that oxidizedindanthrone, monochloroindanthrone and an oligomer of indanthrone are moreefficient saturable absorbers than the parent. Oxidized and monochloro-indanthrone exhibit reversr saturable absorption at both 1064 nm and 532 nm,whereas indanthrone itself exhibits the phenomenon at 532 nm only. Theoligomer, which consists of three anthraquinone units, has proved to be an effi-cient reverse saturable absorber at 1064 nm as well a5 at 532 nm.
1C. R. Giuliano and L. D. Hess, IEEE J. Quantum Elec. QE-3, 338 (1966).
This work was supported in part by the Dept. of the Navy under Contract No.N00039-87-C-5301.
1I
THE PREPARATION AND CHARACTERIZATION OF POLYMERIC MATERIALSWITH ENHANCED SECOND ORDER NONLINEARITLES. M.L. Schilling, H.E.Katz, D.I. Cox, AT&T Bell Laboratories, Murray Hill, NJ 07920.
We have recently introduced a new class of organic materials for second ordernonlinear optics, consisting of poled films of dye-containing polymers. In the pastyear, some uncommon functional groups (di- and tricyanovinyl) have been shown toenhance the molecular susceptibilities of the nonlinear moieties when used instead oftheir more usual counterparts. Dyes with enhanced nonlinearities by virtue of thecyanovinyl substituents have been exploited in the preparation of bulk materials withsome of the highest second order susceptibilities yet reported.
The synthesis of conformationally defined dye aggregates, whose subunit dipolesare constrained to be additive, is in progress. These dyes can then be incorporated intopolymeric materials, taking advantage of their enhanced effective dipole moments forincreased orientation in poling experiments. We will report some of the new syntheticorganic chemistry that has been utilized in preparing our latest electro-opticalmaterials.
A
II
Second Harmonic Generation in Doped Glassy Polymer Films as a
Function of Physical Aging
Hilary ". Hampsch[a', :Jan Yang,'t , George ':. Wcngo,
and John. M. Torkelsonla,c:*
[a! Department of Materials Science and Engineering
't: Department of Physics and Astrzncmy
[c7 Department of Chemical Engineering
and the Materials Research Center
Northwestern University
Evanston, llinois
March 31, 1988
ABSTRACT
The temporal stability of second harmonic generation (SHG;
intensity is measured in poly~methyl methacrylate) (PMMA) and
bisphenol-A-polycarbonate (PC doped with nonlinear optical dyes
in electric field poled films. Doped PC films show slower SHG
decay than doped PMMA films at times less than S hours. In
PC-CANS films aged 10 hours at 250C, there is no SHG decay over
the first 8 hours, whereas in PMMA+DANS aged at 250C and at 60oC
the effect is much smaller. Two dopants show the effect of size
on SHG decay, with the larger dopant showing increased temporal
stability. Good agreement is obtained when decay curves are fit
using a Williams-Watts stretched exponential.
to whom correspondence should be addressed
ELECTRO-OPTIC, POLYMER CLAD, E-FIELD SENSOR
L. MICHAEL HAYDENGERALD F. SAUTER
UNISYS CORPORATION, CSD, St. Paul, MN, 55164
Abstract
There is a military need for sensor systems that combinehigh sensitivity, immunity to EMI/RFI, large bandwidth, and lowpower and cost. The hybridization of present day electroniccomponents with optical components offers the promise of sensorsystems that meet these requirements.
Unisys has been developing a PVDF-coated fiber optic,electric field sensor and now has expanded its program to includenonlinear organic polymers as cladding and waveguide material.This paper will report on progress using Guest/Host (GH) polymersas cladding material.
The concept of an all dielectric high frequency sensor isdemonstrated. The sensor consists of a Ag" exchange waveguidecoated with a GH nonlinear polymer glass. The sensor isincorporated into one arm of a Mach-Zender interferometer andexhibits a figure of merit of 4 microradians/volt/meter/meter.The frequency response is flat from DC to our currentinstrumentation limit of 5 MHz.
This sensor design was chosen primarily as a vehicle thatwould allow an easy method to test and verify design parametersfor fiber sensor systems. These parameters include index anddepth of guide vs. index, thickness and E-O coefficients of thecladding. We will present a comparison of the results of thissensor with those from the PVDF sensor program.
4.)LECUL1%R CONFCRmAT:ON .A!D THE STAB::-:=
TICT STATE :N P,?' -DISUBST:-TUTE-I,6-DIPHENYL-1. 3, 5- HE.TRIENES
C.T. Lin, H.W. Guan, R. K. McCoy and C. W. SpanglerDepartment of Chemistry
Northern Illinois University
DeKalb, IL 60115
ABSTRACT
_The p,p-disubstituted linear diphenyl polyenes are expected to have a highoptical nonlinear susceptibility because of its large permanent dipole momentinduced by the substituents . The photophysical properties for a series ofp,p'-disubstituted-l,6-diphenyl-l,3,5-hexatrienes (referred as DA-DPH) areinvestigated, where D and A are the electron-donating and - accepting groups of-OCH3, -N(CH3 )2 and -NO2. In all solvents used, a dual fluorescence isobserved for D,A-DPH containing the internal rotation groups of -N(CH3 )2 and/or-NO2 , suggesting that the "a*" fluorescence (the locally excited state givesthe normal "b*" fluorescence) is originated from a twisted intramolecularchange transfer (TICT) state. The suability of TICT state is sensitive to theD and A substituents and their relative twisting angles. The observed resultsprovide the evidence of the 7-eLectron distortion and thus the enhancemet: ofoptical nonlinearity in this class of molecules.
Second and Third - Order Nonlinear Optical Properties ofEnd -Capped Acetylenic Oligomers
Joseph W. Perry, Albert E. Stiegman, Seth R. Marder and Daniel R. Coulter
detPrgopus/bn Laboratory, California Instite of Technology480 Oak Grove Drive, Pasadena, CA 91109
We have been investigating the second and third - order nonlinear opticalproperties of avariety of acetylenic oligomers. A series of symmetric acetylenicoligomers of the form
R -(C=C) - R In
have been investigated for third - order nonlinear susceptibility. A series of newcompounds of the form
D- (C=C) -A IIn
where D and A are electron donor and acceptor groups, respectively, havebeen synthesized and investigated for second - order nonlinearity. Third -order nonlinearsusceptibilities of series I molecules in solution have beenmeasured using third harmonic generation (THG). THG susceptibilities at1064 nm have been determined for various oligomer lengths and end - cappinggroups. X(3) increases with length and varies with the nature of the end -group. Series II compounds have been screened for second harmonic gener-ation by using the Kurtz powder method. Several samples show SHG efficien -cies comparable to urea. Characterization of molecular hyperpolarizabilitiesforthe series is in progress.
Optical Field Induced Scattering inPolymer Dispersed Liquid Crystal Films
P. Palffy-Muhoray, Michael A. Lee and J.L. WestLiquid Crystal InstituteKent State University
Kent, OH 44242
ABSTRACT
We report observations of optical field induced scatteringin polymer dispersed liquid crystal films due to reorientation ofthe liquid crystal molecules by the optical field of a CW argonion laser. These composite materials consist of nearly sphericalliquid crystal droplets dispersed in a polymer binder. Aspreviously reported 1,2,3, films of these materials may beswitched from an opaque scattering state to a clear transparentstate by application of a d.c. or low frequency a.c. electricfield. An applied low frequency electric field is used to alignthe liquid crystal in an orientation such that the refractiveindex of the liquid crystal within the droplet is matched withthat of the polymer binder. If a sufficiently intense opticalfield is applied to the transparent film, it will reorient theliquid crystal director, and give rise to a refractive indexmismatch and hence scattering.
1. J.W. Doane, N.A. Vaz, B.-G. Wu and S. Zumer, App. Phys. Lett.
48, 269 (1986).
2. J.L West, Mol. Cryst. Liq. Cryst. (in press).
3. S. Zumer and J.W. Doane, Phys. Rev. A 34, 3373 (1986).
FABRICATION OF WAVEGUIDE STRUCTURES FROM SOLUBLEPOLYDIACZ"YLENES. G.L. Baker, N.E. Schlotter J.L. Jackel, P. Townsend,S.Etemad, Bell Communications Research, Red Bank NJ 07701.
Thin waveguide structures were fabricated from spun films of poly(3-BCMU) andpoly(4-BCMU) by two separate processes. In the first, micron-sized features werepatterned in polydiacetylene films using deep-UV lithography. This multilayer processutilizes a novel silicon-substituted polyacetylene as the resist layer, and can be used togenerate sub-micron sized features in thick (> 1 I m) polydiacetylene films.
In the second method, composite waveguides were fabricated from a patterned glasssubstrate and an overlayer of the polydiacetylene. These composite structures arerelatively simple to prepare and are mechanically robust. Guides constructed asdescribed above performed well with minimal losses and single-moded behavior atlaser wavelengths of 1-1.5 g m.
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