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ポリイミド基板上に作成されたバナジルフタロシアニン薄膜の3次非線形光学強度と形態への有機ガス効果

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愛総研。研究報告

第5号 平 成15年 71

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Vanadyl~

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ポリイミド基板上に作成されたパナジルフタロシアニン薄膜の

3

次非線形光学

強度と形態への有機ガス効果

YounglongJ担 t

GOIO Sawa t t

金 永 龍

f

津 五 郎 什

9

Yoshi戸IkiUchidaT f f

内 田 悦 行

ttt

Kenzo Kojima t t

小 嶋 憲 三

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ao Ohashi t t組 dShizuyasu Ochiai t t

大 橋 朝 夫

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落 合 鎮 康

tt

Abstrnct Vanadyl“抑制ocyanine(VOPc)thinfilms were prepar吋bya molecular beam epitaxy on a poly耐ude

σ

1)叩bs回teat 1500C叩dlenleywere expostodichloroe出 組evaporr25 hours. Their morphologies W巴reinvestigated with VIs凡N spectra and也esurface泊lagesobserved by an atomic force miαoscope

(証明.The VIs/UV spectrum ofVOPc也in臼mbefore the organic gas treatment has a broad ab印刷onshoulder betwe巴:n640組d74伽lffi組d祖 absorptionpeak at 84伽m加出eQ band region. It has be巴nknownsot紅 白at VOPc thinfilm has Phase 1 , II組d

m

.

Phase 1 has two absorption peaks at 680 and 74伽凹司 Phase II and Phase

m

are characterized with absorption peaks at 820 and 830nm, resp巴ctively 刀lerefore,出emorphology having姐 absorption peak at 840nm is di旺巴rent企om出atofPhase

m

.

The VIs凡Nspectrum ofVOPc thinfilm after出巴 org但llCgas仕eatmenthas a broad absorption shoulder between 640組d740nrn and an absorption pωk at 830nrn in the Q band region. The absorption peak at 84印国1shifts to 83伽lffiby也巴organicgas住eatrnen.t官 邸means也at the phase morphology ofVOPc也in日mchanges into Phぉe

m

du血19也egas住eatment. On the0白erh姐dヲ VOPcmoleωles deposited on PI substrate before the organic gas出atmentform needleαystals. This indicates that VOPcmol巴 印lesdeposit吋onPI substrate are perpendicul征toPIsubs加te.百lesUl也氏出lageofVOPc

thin film aft紅 白egas位eatm巴ntlSsmoo白

τ

b

i

s

suggests that VOPc molecules紅epara!lel to PI subs仕at巴 Th巴吐UId-orderoptiω1 susceptibilities after and before吐legas住 関 伽lent紅e3.75x10-9祖d3.25x10-9岱民respectively. 百lemolecular orientation of VOPc thin film is出lproVed出 由19出eorganic gas treatmen.t 1.fut四dnction A vanadylphthalocianine(VOPc) moleωI巴isa dye's molecule. Its πco町ugatedlength is relatively long as compared with other phthalocyanine derivatives and its crysta!mo甲hologyhas a lot of crystal phases. VOPc thinfi1ms as nonlinear optical materials were prepared by moleωlar beam epitaxyl-3). EspeciallぁVOPc thin宣IlllShave been fabricated on sutヲS回tesofa!kali halide crysta!s where VOPc mole四les紅e deposited epitむdally4-5). VOPc mole四les deposited form a commensurate square lattice of 3x3R450 on KBr substrate and 10xl0R:t2ア type and bidirectional orientation for epiaほialsquare lattice on KCl

T

愛知工業大学電気・材料工学専攻 (豊田市) t t 愛知工業大学電気工学科 t t t 愛知工業大学情報通信工学科 (豊田市) (豊田市) substrate1). On the other hand ヲpolymermatelials have excellent high transparency, smooth surfaceラ 批 氾bilityand low price as

mpared wi白afus巴dquartz組dalso an excellent flexibility and low price as compared wi白alkalihalide single crystal substrates. However, few dye's thinfi1ms have been prepared so far on polymer substrates in the :field of nonlinear optical materials. ln 出ispaper, the morphologies and nonlinear optical prop巴r!iesof vanadylphthalocyanine(VOPc) th泊fi1msprep訂edon polyimide substrate were studied with Vis凡九Tspectra, XRD profi1es, AFM 出age,SEM irnage組dthird order nonlinear optical susceptib出ty. 2. ExperimenI5 VOPc fi1ms were fabricated on polir凶desubstrates by the moleωlar beam epitaxy (MBE) method.The source material used was VOPc powder supplied fiom Eastman Kodak Company. Fig. 1 shows

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72

愛知工業大学総合技術研究報告,第 5号 平 成 15年, No.5,M紅 づ2003

the VOPc moJeα11ar struc加re 百lemolecule isl.4nm in diameter

釦d0.2nm in hight. 25問1-thick polyinude film was adopted as a substrate. After VOPc powder was inserted into a Knudsen-cell, it was preheated at 3000C for two hours 立lesubs仕ateof polyinude was attached on the holder just a設erthe cleaIling with acetone.

こ ヤ

7

1

グ¥守守二〉

乙三子夫

- - N

ーベミ壬主

: [ m

二 1.4n m Fig.1 Mol巴cularstruc加reofVOPc molecule

The main chamber of MBE was at about 10←7Pa. The prep紅白g

conditions of samples訂elisted泊Tables1 and 2. Symbols in Tables 1 組d2 are evapora白19temperatur巴・ Te evaporating出ne:t and substrate lemperature: Ts・ S-1-12means Samples 1-12. The

thiclrne路 ofS -1-6 are 96, 102, 108, 95ヲ 98組d 104nmヲ respectivel

y

.

官 官thicknessof S -7-12 are 96ヲ108,139, 94, 97 and 108nm, respectively. 百leincident angle dependence of third Table 1 Preparing conditions ofVOPc thin films Sarnple no. 1 2 3 4 5 6 T e[o

C

]

300 Ts

[

O

c

J

25 t

[

m

i

n

J

.

60 120 180 60 120 180 Organic gas N N N Y Y Y Treatment Table2Prepぽing

nditions ofVOPc thin且lms. Sampleno. 7 8 9 10

1

1

12 T e[o

C

]

300 Ts

[

O

c

J

150 t

[

m

i

n

J

60 120 180 60 120 180 Organic gas N N N Y Y Y

τ

I'eatment

harmonic(

百1)

intensi臼esof S -1-12 are measured by Maker創nge with Nd YAG laser. Its specifications are output 455mJ, wavelength 1064nmヲpulsewidth 5ns and repeating金equency10Hz, respectively 百le third harmonics is detect巴d wi出 a photomultiplie.r 3. Results and Discussi由][1 Fig. 2 shows theVi.s川V spectra of Samples 1 10 3 before org拙 C gas treatm巴ntand Samples 4 to 6 after. Samples 1 to 3 have抑o absorplion shoulders a! 680 and 820 nm釦d釦 absorptionpeak at 740 nm 百lemorphology having a long broadband around 730 and an absorption peak at 680 nm was named Phase I by Gri血ths et.a]..百lemorphology having a long broadband around 730 and two absorption peaks at 680 and 820 nm was also named Phase

I

I

Therefore, th巴y血dicale出atthe VOPc thin films of S但nples1 to 3 were deposited initially with Phase

I

I

, and then前thPhas巴Ion Phase

I

I

司 On the other handヲIheVOPc白血filmsof Samples 4 10 6 after the orgamc gas treatment have組 absorptionpeak at 820nm 組da畳atabsorption band企om650 10 780 nm. As described above,

themo中hologyof Samples 4 10 6 is near Phase

I

I

.

The absorption

、 v 1l 禍 唱 粋 P ω 中 川 γ 仁 何 一 U て 日 々 バ 的 3 く

0

5

n

凡 山 口 t J GOJi

7

C

O

7

5

0

:

3

5

0

~I ClO Fig. 1 Vis(UV spectra of Sampl巴s110 6. shoulder丘t820 nm of Samples 1 10 3 befor巴theorganic gas lreatment changes血10 an absorption peak at 820nm after the organic gas treatmen.t VOPc molecule is donor6). If 1,2-Dichloroethane is acceptorηヲ the donor-acceptor interaction betw巴 町VOPcmolecul巴 組d1,2-Dichloroethane causes a higher moleαl征 d曲lsion a責任 批 organic gas treatmenl and it accelerates to change from Phase 1 10 Phase

I

I

Fig. 3 shows AFM irnage of Sample 3. 百lesu由C巴ofVOPcthin

臼mdeposited on the poly皿 desubstrate kept at 250C is smooth. It

(3)

ポリイミド基板上に作成されたパナジルブタロシアニン薄膜の3次非線形光学強度と形態への有機ガ、ス効果 73 molecules deposited on a polyethreylene-terephthalate(pET) substrat巴is31kcallmol

りIt

svalue is higher than that of the hydrogen bonding. Polyimide組dpolyethreylene-terephthalate :fi1ms訂earomatic polymer 百lef巴fore,the且ctivationenergy of desorption of VOPc molecules on the PI substrate is expected 10 be m訂 thevalue on the PET substrate. Moreover, the interaction of

between VOPc mole四leson the PI subs国 民isbelow 10 kcal/mol and the molecular d出 国onof VOPc moleαles on the PI substrate kept at 25

O

c

is Iow. These reveal that VOPc molecules deposited on the PI substrat巴 紅ep訂allelon白esubstrate.

Fig. 4 shows the AFM image of Sarnple 6. A 101 of island crystals are observed on the PI substrate. The mole四lard臨 時ionofVOPc moleαlles oc印 路onthe PI substrate kept at 150oC. Therefore, it 担dicatesthat a lot of island cηstal grow with merging gr四 Sof 今 J P A m p 品

σ 白 血 M

m

今 、 J σ 白 官 A

Fig.4 AFM image of Sample 6.

0.01

L

亙ちり空

1 <)5

両 主 主 盃 司

島h 量弘 A 色白色皇弘 治 臨 ー&

:もご号、ト色

&昌弘 占弘昌弘昌弘昌弘 AI!ir鍾 [ , コ E 伺 ] 同 一 戸 一 凹 戸 ﹄ 由 主 一 エ ト 0 50 -30 -10 10 30 Incident angle [deg.] 50 Fig.5在Iintensity vs. incident angl巴ofSamples lto 3.

す0.01

'

"

] 』 +" (fJ E ω 斗~ E 工 ト 0 -5

0

O Incident angle [deg.] 50 Fig.6百1intensities vs. incident angle of Samples 4 to 6 VOPcmoleαles on the substrate. 百lisindicates that the packing density of crystals of Sample 6 is higher than that of Sample 3. In other words, Sample 3 is a VOPc白血宣1mdeposited dominantly with Phase 1 and Sample 6 is deposited dominantly with Phase

I

I

.

From Vis凡凡

r

spectra and AFM images, the phase mo中hologyof S出nples1 to 3 are dominated with Phase 1 and Sampies 4 10 6 are

dominated with Phase

I

I

. 百ledistan

between layers of Phase 1 is larger出anthat of Phase

I

I

官 邸 meansthat the electron

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74

愛知工業大学総合技術研究報告,第5号 平 成15年,No.5ラM札 2003

harmonic intensity depend upon血eecleclron density between lay巴rsof Phase. Thereforeヲ itis expected that1H intensity of

Phase

I

I

is I紅gerth組 thatof Phase

1

.

IfSamples 1 to 3紅E dominated with Phase

1

and Samples 4 to 6 are dominated with Phase

I

I

,也巴thirdharmonic加tensityof Samples 1 10 3 are lower

than those of Samples 4 10 6. Fig. 5 shows TII intensity vs. incident angle of Samples 1 to 3 irradiated with P pol紅izedlaser

Iight(Laser sour∞: ND: YAG laser, Wavelength: 1064 nm). Fig.6 shows官Iintensity vs. incident angle of Samples 4 10 6. Samples 1,2 and 3 hav巴small1H血tensitiesas comp紅 巳dwith Samples 4, 5

and 6, respectively. These indicate Ihat Samples 1 to 3 have Phase

1

and Samples 4 10 6 have Phase

I

I

1 .5 ω o c c ﹄ ﹂ O ω ﹄ ︿

o

.5 500 550 600 650 700 750 800 850 900 Wav巴length [nml Fig. 7 Vis/UV sp巴ctraof Samples 4 to 9. Fig冒7shows theVis川V spectra of Samples 7 to12. The Vis,川V spec回 ofSamples 7 to 9 have a simil紅 pa抗em. 百leVis川V spectrum of Sample 7 has却 absorptionpeak at 840 nm組 da f1at

broad band 企om650 to 780 nm. 百le absorption peak of Samp巴l<s7 to9 shifts by 20 nm to the longer wavelen凶1side th組

those of Samples 10 to 12. 百lerefore,the mole印lard出lsionof

VOPc molecu1es deposit巴don PI subs仕atekept at 1500C may

redu

the activation energy of absorption between VOPc moleαIle and PI subs回leso that the interaction between VOPc molecules is lager th叩 thatbetween VOPc moleα11e佃dPI substrate, and VOPc

mol巴αlles are perpendiωl紅 on PI substrate bec且use of the interaction be抑een VOPc molecules.τbis means出at the moleωl紅 packingdensity of the VOPc mole印lesperpendiαllarly

oriented on PI subs回teis high紅 白anthat of parallel-oriented one Fig. 8 shows the AFM image of Sample 9. A lot of needle crystals are observed町 τmsreveals that VOPc mole印les訂eperpendicular

Fig. 8 AFM image of Sample 9目

Fig.9 AFM image of Sample 12.

0目 白PIsubstrate. vi叫JVspectra of Samples 10 10 12 have a similar pa抗em. For巴X且mpl,巴Sample 10 has組 absorptionpeak at

830 nm and a :I1at broad band企om650 to 780 nm. An

absorption peak in theQ band region of SampJe 10 after the org削 C treatment shifts by 10nm 10社lelower wavelength side than that of Sample 9. 11ris means that the activation energy of abso甲tionof VOPc moleαles deposited on the PI substrate increases with the orgar討cgas treatmen.t Fig司9shows the AFM image of Sample 12 τbe surface of VOPc thin film has a 101 of grむns. Its surface is 5泊illar10 the surface of the VOPc crystal films deposited on泣kali halide substrates. This suggests that the absorption energy h阿eenVOPc mole叩l巴andthe surface of PI substrate after the organic gas treatment increas岱 wi血adonor-acceptor interaction and VOPc moleαIles ar巴depositedparallel on the PI substrate. Fig. 10 shows the incident angle dependence of百1intensity for Samples 7 to 9. They show upper

nvex curves centered at 0 degree and increase with increasing the thickness of Sample.

These indicate that the orientation of VOPc molecules deposited on

(5)

75 ポリイミド基板上に作成されたパナジルフタロシアニン薄膜の

3

次非線形光学強度と形態への有機ガス効果 thickness. On the other hand, for the VOPc白血filmsprepared at 1500Cit sa他rateswith the泊creaseof出icknessbefore出eorgaruc gas treatment (Sample 7, 8 and 9)ヲbutnot after the gas treatmen.t 百llSmeans that Samples 10 to 12 have an excellent high order orientation. The白 凶ordersusceptibility

(

i

3) ) of Samples9 and 12 prepared on the PI substrate kept at 1500C are estimated from the maximum TH inten均 at0 degree. The

0

3) values after and before白egas treatment (Samples 9組d12) are3.75x

w

-

9祖d 3.25x10-9 esurespectively.τbis indicates that the orientation of VOPc白in:film is improved by the orgarric gas treatmen.t

l

山 foreorganic gas tre

関Beforeorganic gas treatment at 1500C

い為

Afterorganic gas treatment at 250C LOAfter organic g

:

a

__!reatment at1500C

m g L 噌 l n u n u n H u n H U [コ伺 ] h H 一ω E ω 判 E 一 工 ト E コ E 一 × 何 一 孟 of Samples 7 to9 is a higher order orientation仕1anSample 1 to 3 and a higher packing density tharr that of Sarnples 1ω3. Fig.11 shows the incid巴ntangle dependence of百-Iintensity for Samples 10 to 12. As mentioned above, the orientation of Samples 10 to12 has an巴xcell巴ntmole印 旭 町 組gementas compared with Samples 7 to9. Therefore, 1H血tensitiesof Samples 10, 11 and 12紅巳 larger白anthose ofSamples 7, 8 and 9フrespectively. 0.02 ,..., コ ro '--' 〉、

0β1 c Q) +' C Z ト

-5

0

-10 10 30 50 Incident angle [deg.] -30 Fig.101H intensity vs. incid巴ntangle of Samples 7 to 9.

250 200 100 150 Thickness [nml 50 Fig.12m犯 血um1H intensity vs. thickness. τbe phase morphology ofVOPc thin film on PI subs回techanges 企omPhase

1

to Phase

I

I

by the organic gas treatment absorption energy be帆reenvOPc moleαlle and白esurface of PI substrate increases with gas treatmen.t The vOPc thin film pr巴P訂ed on PI substrate kept at 1500C is dominated with perpendicular mole印lぽ orientation but changes 10 p征allel molecular orientation after the gas仕ぬtmen.t Theχ(3) value of VOPcthin五1mprepared on PI substrate kept at 1500C is estimated from the m鉱 出um1H intensity measured by Maker金也ge司 百1e

P

)

values before組dafter the gas trea団 副 都 3.25x10-9and 3.75xlO-9 esu

respectively. It is improved during the organic gas 官 邸 paperwas published by APOC2002 h巴ld on 百le 4.Conclusions 50

hUD

I-ihiiI

& 0.02 30 10 Incident angle [deg.] 品 ゑ A 、J -10 く 〉 弘 -30 0.01 0 -5

0

[ コ 伺 ] h H Z C U H C 一 エ ト treatment China. Fig.ll耳Iintensity vs. incident angle of Samples 10 to 12. Fig. 12 shows白emaximum 1H intensity as a function of thickness. 百lemaximum 1H担tensityfor VOPc thin films prepared on th巴PI substrate at2SoC has a tendering to saturate w抽 theincr巴aseof

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76 愛知工業大学総合技術研究報告,第5号 平 成 15年ヲ No.5,M札 2003 Admowledgment

τ

'he pres巴ntwork was partly supported by a grant of the Frontier R蹴 arch Proj ect

Materials for批 21stCen旬ry -Materials Development for Environment, Energy andInformation _" (for 2002-2006 fisω1 ye紅s)from Ministry ofEducation, Culture, Sports, Scienc巴 組dTechnology. Refe官nr.ces [1]. H. Tadaフ K Sakai andA. Koma,“Preparation and characterization of vanadyl-phthalocyanine ultrathin :film grown on KBr nad K O by mole印l紅beamepitaxy, "争n.J.App.lPhys.

30, pp. 1306-308 (1990)

[斗主MoriokaヲH.Tada and A Koma, "Altemative h巴teroepit氾aal

grow血ofvanadyl-and chloroalumnum-phthalocyanine on KBr and K O,"J.App.lPhys. 73, pp.2207-2214 (1993) [3]. H. Hoshi and Y Maruyama

Ep社位ial growth of chloroaluminum and vanadyl phthalocyanine films on alkali halide single crystals by the moleωlar-bearn-ept沼 iytechnique

"

J.App.lPhys. 69フpp.3046-3052 (1991) [4]. H. Hos, Kih .Hamamoto, T.Yarnada, K Ishikawa, H. Takezoe, A FukudaフS.Fang, K.Kohama組dH. Takezoe,“百uckness

dependence of the epitaxial struc佃reof v組adylphthalocy紅 町 民

団m,"Jpn. J.App.lPhys. 33, pp.L1555-1558 (1994)

[5]. S. Fang, H. Tada and S. Mashiko,“Enhancement of the third-order nonlinear optical susceptib出ty in epitaxial vanadyl-phthalocyanine films grown on KBr,"

Ap

p. Phys. Lett., 69

pp.767-769 (1996)

[6]. Qiu,LShen Y二Q,Xu H-J, Zhang Z-X, Yie P-X, Yu組 P,XiaZ-J 組d

z

o

叩u Y芋~H且, No凶血E訂担i担悩tie侭:s 0ぱf Soluble Va釦na吋dy升I P到thlo勾cya却n血E侭s"ヘInsはt.

.

Ph加otωogra叩phicChenustry andIns.tPhysics, Chin巴seAcad Sci.,B吋ing,Peking U旭川Beij血gヲ55(1997)

[

.

M. Tanakaヲ Phthalocyanine,Bunnshin Publication, Tokyo, Japan, 1997 (Japanese)

[8]. T. Souma, H. Furuhashi, T.Yoshikawa, A. Maeda, Y Uchida, K kojima, A Ohashi, S. Ochiai組dT. Mizutani,“Nonlinear optical

properties and morphologies of vanadyl怯phthalocyanine白血films

prepared on poly巴thylene-terephthalate曲n,"T.AE;'叩 叫 121-C pp.1171-1178 (2

1)

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