(12) united states patent (10) patent no.: us 7,524,611 b2 ... · us. patent apr. 28,2009 sheet 2...

US007524611B2

(12) United States Patent (10) Patent No.: US 7,524,611 B2 Bel?eld (45) Date of Patent: Apr. 28, 2009

(54) PHOTOSENSITIVE POLYMERIC MATERIAL JP 200302756 10/2000 FOR WORM OPTICAL DATA STORAGE

WITH TWO-PHOTON FLUORESCENT OTHER PUBLICATIONS

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READOUT

Inventor: Kevin D. Bel?eld, Oviedo, FL (US)

Assignee: University of Central Florida Research Foundation, Inc., Orlando, FL (US)

Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 37 days.

Appl. No.: 11/904,287

Filed: Sep. 26, 2007

Prior Publication Data

US 2008/0187862 A1 Aug. 7, 2008

Related U.S. Application Data

Division of application No. 11/256,552, ?led on Oct. 21, 2005, noW Pat. No. 7,291,442, Which is a division ofapplication No. 10/306,960, ?led on Nov. 27, 2002, noW Pat. No. 7,001,708.

Provisional application No. 60/339,283, ?led on Dec. 11, 2001, provisional application No. 60/333,972, ?led on Nov. 28, 2001.

Int. Cl. G03F 7/004 (2006.01) U.S. Cl. ................... .. 430/270.1; 430/922; 430/926

Field of Classi?cation Search ............ .. 430/270.1,

430/922, 926 See application ?le for complete search history.

(56) References Cited

U.S. PATENT DOCUMENTS

4,458,345 A 7/1984 Bjorklund et a1. 5,253,198 A 10/1993 Birge et al. 5,268,862 A 12/1993 RentZepis 5,289,407 A 2/1994 Strickler et al. 5,770,737 A 6/1998 Reinhardt et al. 5,859,251 A 1/1999 Reinhardt et al. 5,912,257 A 6/1999 Prasad et al. 6,100,405 A 8/2000 Reinhardt et al. 6,267,913 B1 7/2001 Marder et a1. 6,310,850 B1 10/2001 Sochava et al. 6,696,216 B2 * 2/2004 Li et al. ................. .. 430/270.1

6,822,384 B2 * 11/2004 Huang et al. . 313/483 7,206,111 B2 * 4/2007 Huang et al. .............. .. 359/239

2001/0018099 A1 8/2001 Gibbons et al. 2001/0028620 A1 10/2001 Guerra 2001/0030934 A1 10/2001 Lipson et al. 2002/0160282 A1* 10/2002 Huang et al. ................. .. 430/7

2005/0271971 A1* 12/2005 Ueda et al. ............. .. 430/270.1

JP JP JP JP

FOREIGN PATENT DOCUMENTS

62-244058 10/1987 62-244059 10/1987 11-144873 5/1999 11-185966 7/1999

P. Cheben, et al. A photopolymerizable glass with diffraction ef? ciency near 100% for holographic storage, Apl. Phys. Lett. Mar. 12, 2001, vol. 78 No. 11, pp. 1490-1492. K. Bel?eld, et al., Methodology for the Synthesis of New Multifunctional Polymers for Photorefractive Application, in Field Responsive Polymers, ACS, Symposium Series 726, American Chemical Society, pp. 250-263. K. Bel?eld, et al., “Two-Photon photochromism of a photorefractive organic material for holographic recording” Proc. SPIE-Int. Soc. Opt. Eng, 2000 ( in press )7 pgs. Jong-Man Kim, “Photoacid-Induced Fluorescence Quenching: A New Strategy for Fluorescent Imaging in Polymer Films” Angew. Chem. Int. Ed. 2000, 39, No. 10, pp. 1780-1782. K. Bel?eld, et al., “Multiphoton-absorbing organic materials for microfabrication, emerging optical applications and non-destructive three-dimensional imaging” J. Phys. Org. Chem., 2000, 13, pp. 837 849. W. Denk, et al., Two-Photon Laser Scanning Fluorescence Micros copy, Science, vol. 248, pp. 73-76. R. Birge, et al., “Protein-based Three-dimensional Memories and Associative Processors” in Molecular Electronics, Chapter 15, pp. 439-472. K. Bel?eld, et al., “Three-dimensional two-photon imaging in poly meric materials” SPIE 2001 (submitted) 9 pgs. D. Parthemopoulos, et a1. “Three-Dimensional Optical Storage Memory” Science, vol. 245, Aug. 25, 1989, pp. 843-845. G. Pohlers, et al., “A Novel Photometirc Method for the Determina tion of Photoacid Generation Ef?ciencies Using BenZothiaZole and Xanthene Dyes as Acid Sensors” Chem. Mater. vol. 9, No. 12, 1997, pp. 3222-3230.

(Continued) Primary ExamineriJohn S Chu (74) Attorney, Agent, or FirmiBrian S. Steinberger; Joyce Morlin; LaW O?ices of Brian S. Steinberger, PA.

(57) ABSTRACT

Image formation via photoinduced ?uorescence changes in a polymeric medium With tWo-photon ?uorescence readout of a multi-layer structure. Fluorophore-containing polymers, possessing one or more basic functional groups, underwent protonation in the presence of a photoinduced acid generator upon exposure to a broad-band UV light source or fast-pulsed red to near-IR laser irradiation. Solution studies demonstrated formation of monoprotonated and diprotonated species upon irradiation, each resulting in distinctly different absorption and ?uorescence properties. The ?uorescence of the original, neutral, ?uorophore Was reduced upon monoprotonation, leading to a concomitant increase in ?uorescence at longer Wavelengths due to the monoprotonated form, the basis for multichannel data readout. Experiments in polymer ?lms demonstrate the changes in ?uorescence properties of the photosensitive polymer compositions and polymers can be employed for a high storage density, Write-once read-many (WORM) data storage medium With tWo -photon ?uorescence readout. TWo -channel, tWo -photon ?uorescence imaging pro vided both “positive” and “negative” image readout capabil ity.

2 Claims, 12 Drawing Sheets

US 7,524,611 B2

OTHER PUBLICATIONS

K. Bel?eld, et al., “Synthesis of New Two-Photon Absorbing Fluorene Derivatives via Cu-Mediated Ullmann Condensations” The Journal of Organic Chemistry, vol. 65, No. 15, Jul. 28, 2000, pp. 4475-4481. K. Bel?eld, et al, “New Two -Photon Absorbing Fluorene Derivatives: Synthesis and Nonlinear Optical Characterization” Organic Letter, 1999, vol. 1, No. 10, pp. 1575-1578.

K. Bel?eld, et al., “Modi?ed Horner-Emmons Reaction of Polymeric Phosphonates: Versatile Synthesis of Pendent Stilbene-Containing Polymers” Journal of Polymer Science, Part A, Polymer Chemistry, 1995, vol. 33, pp. 1235-1242. K. Bel?eld, et al., A New Photosensitive Polymeric Material for WORM Optical Data Storage Using Multichannel Two-Photon Fluo rescence Readout, Chem. Mater. 2002, 14, pp. 3656-3662.

* cited by examiner

US. Patent Apr. 28,2009 Sheet 1 or 12 US 7,524,611 B2

H I Q CIGHII CiDHZI N B‘ Q CIDHZI CmHz: N+

*?ibs? * Wiibw? S S

Q 1 C; 2 km,‘ absorption == 500 nm in, absorption =390 um 1..., emission = 625 nm km, emission =60 um

H ‘ Q CmHn C1052: }|{+

_H_. New D J’ 5

® 3 1,”, absorption = 376 nm

in, emission = 445 an

Figure i shows the reaction of ?uorene dye 1 Wiih acid resulting in the

formation of monoprotonated 2 and diprotonated 3 products.

0.20 ~ ' '-.

0.15 '

11.10 - Absnrhimce 0.05 >

350 4G0 450 $00 550 600 650

Wavelength (n m)

Figure 2 is a graphical representation of the time-dependent UV-visible

absorption spectra of ‘the photolysis of ?uorene 1 and photoacid generator in

CH2C12 at photolysis times from 0 to 120 sec.


Intensity (countslsec)

Wavelength (nm)

Figure 3 is a graphical representation of the time-dependent fluorescence

emission spectra for the photolysis of ?uorene land photoaeid generator in

CHICIZ at photolysis times from 0 to 120 sec (excitation at 390 nm) with an

inset that shows ?uorescence at longer wavelength with excitation at 500 nm.

Figure 4 Two~phot0n upconverted ?uorescence emission spectra of l at several

fs pulsed pump Wavelengths (2.5 x 10 “4 M, ACN).

US. Patent Apr. 28, 2009 Sheet 3 0f 12 US 7,524,611 B2

3.5

, -- 3

i , Ar " f; - ‘ ? -- 2.5

i; a ' ' " 2

f5’ -- 1.5 H

In - 1 5 " '- - Pump: 79011111 (slope=1.B6) __ 0 5

Pump: 730 nm (slope=2.?8) ' f . . . t 0

4.4 -1.2 -1 41.8 40.6 414 Log Pump Power

Figure 5. Plot of the total integrated ?uorescence intensity of 1 as a function of

pump power at two fs pump wavelengths.

an n» p, m

Iauh-A an:

Figure 6. Photoacid generation and time-dependent absorption spectra of PAG.


m5 intern». ,2

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‘Group 3, elements 4. 5. 6 of target (73.7 pm. element 5}

' ' Elm ihiclmess: 1.196113“

pm

' Fluorescent image of exposed arm

‘Channel 1 detector: (green) Em from SID to 550 nm

Fiancee-cc emislion iumuily vs. pnsi?nn ‘

Figure 9. Two-photon ?uorescent-images of photosensitive ?lms developed

(via 350 nm broadband exposure, 4.4 rnW/cm2) using an Air F orce resolution

target mask. Image recorded by channel 1 at various exposure times. Data

readout as a function of exposure time determined ?‘om ?uorescence intensity

by scanning an xy line across one set of three-member elements (yellow line

across set 5).


' he! = 800 nm‘ 113 8.1!):

~ Group 3. elements 4, 5. 6 of target {78.7 pm)

- Film thickness:

2.l96i?.045 pm

' Fluoracent image of exposed area

' Channel 2 detector: (org) Em from 585 to 630 nm

Fluorescence emission intensity vs. position

mum’ (-mama» 30 min 60 min:

Figure 10. Two-photon ?uorescent images of photosensitive ?lms developed

(vie 350 nm broadband exposure, 4.4 mWIcmZ) using an Air Force resolution

target mask. Image recorded by channel 2 at various exposure times. Data

readout as a ?mction of exposure time determined from ?uorescence intensity

by scanning an xy line across one set- of three-member elements (yellow line

across set 5).


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5472522231543 piwtcrm

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OSDIIIIZSDIIPZS‘JNEDJUJQ mew-mm

S0 100 Lil 3M

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Wm TEM mo

Figure 13. (a) Two-photon ?uorescent images of multi-layerecl ?lms developed

via 350 nm: broadband irradiation (6.0 mw/cmz) by exposure through TEM

hexagonal and square grid masks. Fluorescence intensity plots for a line scan

across a region (as de?ned by the yellow line across the image area) provides

(b) image readout in one layer, and (c) changing the depth (2 position) for

image (signal) readout in the lower layer Within a multi-layered system.


can ‘"11

Figure 15. Absorption and ?uorescence emission spectra-of polystyrene based

photosensitive poiymers with and without PAG.

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’ 0 mu:

5 ‘ 0 ~un~mam

IOI “WPWIN

in 1 / u .

\ 0.05 4U 0,“ {1 (LB

:- an Mun-M’

Two'pheton upconvcrted ?uorescence cmbsion Emission intensity dependence spectra as a function of excitation wavelength. (2.5 x 10" M, ACN)

Figure 16. Two-photon upconverted ?uorescence emission spectra of

polystyrene based photosensitive polymers, and demonstration of two~photon

absorption via quadratic intensity dependence.


SPERM ?r'nsimspdndlinld “cm W). (Bum)

mm “mm Tue-photon Wzmd ?auum lpecunvofhkled .E m‘; ____3gm Payqeltqlznewkk mm) W‘

n \

E m l ‘J l

a =

m m

Figure 17.‘ Single-photon and two-photon upconverted ?uorescence emission

spectra of polyethylene based photosensitive polymers.

Figure 18. Two-photon ?uorescence image of the exposedophotosensitive

polymer without PAG is shown (le?), along with the ?uorescence intensity

pro?le through the bulk (xyz scan) of the ?lm.

Figure 19. Two-photon ?uorescence image of the exposed photosensitive

polymer with PAG is shown (left), along with the fluorescence intensity pro?le

through the bulk (xyz scan) of the ?lm.


wiemm me we

Flaorescmce intensity pint across yellow line as de?ned in ?lm win PAC

Figure 20. Two-photon ?uorescence image of the exposed photosensitive

polymer without and with PAG are shown (left and right, respectively), along

with the ?uorescence intensity data readout.

Twu-pkuton ?uorescent images Imaging through ?lm thickness 800 um, 113 Is zyz Fiaurscenx intensity pints

Without PAC

Figure 21. Two?photon ?uorescence image of the exposed photosensitive

polymer Without and with PAG are shown (top and bottom, respectively),

along with the 3-D ?uorescence intensity data readout.

US. Patent Apr. 28,2009 Sheet 12 0112 US 7,524,611 B2

Figure 22. Demonstration of two-photon writing and readout in

photosensitive polymer.

Olympus [X-70 inverted microsco r

Ar Sump]:

(4;: nm) Z-motorized stag:

F bObjective XY galvanomezer

1 ........... ._ i Third shame!

(7004000 m) / 1; I I I nondescanned

_ Coherent 10 W Verdi E E i CCD detector and fcmtosecond Mira ".- _:" 4mm

gPMTJ:i 5~1=MT1l a i i I

Modi?ed Olympus F luovicw ' ’ '

XY scanning unit and two channel / = Dmhrorc mu'mr descanned detectors

Figure 23. Schematic diagram of two-photon writing and recording system.

US 7,524,611 B2 1

PHOTOSENSITIVE POLYMERIC MATERIAL FOR WORM OPTICAL DATA STORAGE WITH TWO-PHOTON FLUORESCENT

READOUT

This is a Divisional PatentApplication of US. patent appli cation Ser. No. 11/256,552 ?led Oct. 21, 2005 now US. Pat. No. 7,291,442, Which is a divisional application of US. patent application Ser. No. 10/306,960 ?led Nov. 27, 2002, now US. Pat. No. 7,001,708 B1, Which claims priority of US. Provisional Patent Applications 60/339,283 ?led Dec. 11, 2001 and 60/333,972 ?led Nov. 28, 2001.

FIELD OF THE INVENTION

This invention relates to optical data storage and more particular to a novel photosensitive polymeric material for Write Once Read Many times (WORM) optical data storage With tWo-photon ?uorescent readout.

BACKGROUND OF THE INVENTION

Over the past 50 years, the ?eld of organic photochemistry has produced a Wealth of information, from reaction mecha nisms to useful methodology for synthetic transformations. Many technological innovations have been realiZed during this time due to the exploits of this knowledge, including photoresists and lithography for the production of integrated circuits, photocharge generation for xerography, multidimen sional ?uorescence imaging, photodynamic therapy for can cer treatment, photoinitiated polymerization, and UV protec tion of plastics and humans through the development of UV absorbing compounds and sunscreens, to name a feW.

The scienti?c basis of many of these processes continues to be utiliZed today, particularly in the development of organic three-dimensional optical data storage media and processes.

With the ever-pressing demand for higher storage densi ties, researchers are pursuing a number of strategies to develop three-dimensional capabilities for optical data stor age in organic-based systems. Among the various strategies reported are holographic data storage using photopolymeriZ able media (Cheben, P. and Calvo, M. Appl. Phys. Lett. 2001, 78, 1490; US. Pat. No. 5,289,407 and US. Pat. No. 6,310, 850), photorefractive polymers (Bel?eld et al. Field Respon sive Polymers, ACS Symposium Series 726, ACS, 1999, Chapter 17), and tWo-photon induced photochromism (Bel?eld et al. Organic Photorefractives, Photoreceptors, and Nanocomposites, Proc. SPIE Vol. 4104, 2000, 15-22; US. Pat. No. 5,268,862). It is knoWn that ?uorescent properties of certain ?uorophores may be changed (quenched) upon pro tonation by photogeneration of acid (Kim et al. AngeW. Chem. Int. Ed. 2000, 39, 1780). Bel?eld et al. J. Phys. Org. Chem. 2000, 13, 837 has reported tWo-photon induced pho toacid generation using onium salts and short pulsed near-IR lasers in the presence of a polymeriZable medium, resulting in tWo-photon photoinitiated cationic polymerization. The inherent three-dimensional features associated With tWo-pho ton absorption provides an intriguing basis upon Which to combine spatially-resolved, tWo-photon induced photoacid generation and ?uorescence quenching With tWo-photon ?uorescence imaging.

The quadratic, or nonlinear, dependence of tWo-photon absorption on the intensity of the incident light has substantial implications (dW/dt oc I2). For example, in a medium con taining one-photon absorbing chromophores signi?cant absorption occurs all along the path of a focused beam of suitable Wavelength light. This can lead to out-of focus exci

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2 tation. In a tWo-photon process, negligible absorption occurs except in the immediate vicinity of the focal volume of a light beam of appropriate energy. This alloWs spatial resolution about the beam axis as Well as radially, Which circumvents out-of-focus absorption and is the principle reason for tWo photon ?uorescence imaging (Denk et al. Science 1989, 248, 73). Particular molecules can undergo upconverted ?uores cence through nonresonant tWo-photon absorption using near-IR radiation, resulting in an energy emission greater than that of the individual photons involved (upconversion). The use of a longer Wavelength excitation source for ?uores cence emission affords advantages not feasible using conven tional UV or visible ?uoresence techniques, e.g., deeper pen etration of the excitation beam and reduction of photobleaching, and is particularly Well-suited for ?uores cence detection in multilayer coatings. US. Pat. No. 5,268,862 reported tWo-photon induced pho

tochromism of spiropyran derivatives at 1064 nm. Analogous to single-photon absorption facilitated isomeriZion, the spiro pyran underWent ring-opening isomeriZion to the ZWitteri onic colored merocyanine isomer. The merocyanine isomer underWent tWo-photon absorption at 1064 nm, resulting in upconverted ?uorescence. HoWever, spiropyrans are knoWn to undergo photobleaching and photodegradation upon pro longed exposure With blurring effects observed outside the irradiated volume, and hence are not suitable for long-term use. US. Pat. No. 5,253,198 disclosed a bacteriorhodopsin based holographic recording media and process, using tWo photon excitation. High data storage and photostabilities Were repored for this rather complex system, hoWever it requires near-Zero gravity conditions for processing to ensure homogeneous distribution of the bacteriorhodopsin, an elec trochemical system to measure the electrical response vs. a purely optical response, and careful handling of the biological material (the protein). Though the read time claimed of 100 ns is impressive, as are read data rates of up to 10 Mbit/ sec, the complexity of the system seriously undermines any practical potential applications of the system.

Thus, in addition to high data storage volume and fast readout, there is a need for data storage materials that are stable, highly responsive, exhibit high sensitivity and ?delity, and are less complex. In addition, the data storage and readout processes must also be more straight forWard (less complex) and reliable. As mentioned above, the previously developed systems fall short in these regards.

SUMMARY OF THE INVENTION

The invention described herein relates to high density ran dom access data storage, and is particularly more directed to materials for an optical memory system in Which near-IR laser light is employed to Write and read data via tWo-photon processes Within an irradiated area Which can be controlled in three-dimensions.

It is an objective of the invention to develop a high density optical data storage system in Which optical properties of the medium can be modulated and read in three-dimensions via tWo-photon processes.

Another object of the invention is to develop optical mate rials to enable tWo-photon induced photochemical changes suitable for tWo-photon ?uorescent readout. Another object of the invention is to harness the high pho

tosensitivity of the photosensitive polymers to create a high density optical data storage system With multichannel readout capability to further increase data storage and readout versa tility.

US 7,524,611 B2 3

Another object of the invention is to incorporate structural constructs of the ?uorophores into polymers, creating photo responsive polymers With extraordinarily high photosensitiv ity. A preferred embodiment of the invention is the use of a

photosensitive polymeric material for WORM optical data storage With tWo-photon ?uorescent readout comprising ?uo rophore compounds of the present invention admixed With a polymer. Further preferred embodiments of the invention include (1) a WORM optical data storage device suitable for imposing information on it comprising a disk structure suit able for structurally supporting a polymer ?lm containing about 0.01 to 5.0 Wt % of the ?uorophore and about 0.5 to about 20.0 Wt % of photoaid generator (PAG), relative to the polymer and said polymer ?lm supported by said disk struc ture and (2) said optical data storage device in a readable state Wherein said polymer ?lm has been irradiated to decrease the ?uorescence concentration of the neutral ?uorophore and increase the ?uorescence of monoprotonated ?uorophore Whereby the resulting stored optical information can be recovered via multichannel readout.

Several of these ?uorophores and polymers undergo sub stantial changes in the absorption and ?uorescence spectral properties in the presence of strong acid, i.e., they undergo protonation, affording changes in their polariZability, absorp tion and emission maxima and ?uorescence quantum yields.

Further objects and advantages of this invention Will be apparent from the folloWing detailed descriptions of pres ently preferred embodiments Which are illustrated schemati cally in the accompanying drawings.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shoWs the reaction of ?uorene dye 1 With acid resulting in the formation of monoprotonated 2 and diproto nated 3 products.

FIG. 2 is a graphical representation of the time-dependent UV-visible absorption spectra of the photolysis of ?uorene 1 and photoacid generator in CH2Cl2 at photolysis times from 0 to 120 sec.

FIG. 3 is a graphical representation of the time-dependant ?uorescence emission spectra for the photolysis of ?uorene 1 and photoacid generator in CH2Cl2 at photolysis times from 0 to 120 sec (excitation at 390 nm) With an inset that shoWs ?uorescence at longer Wavelength With excitation at 500 nm.

FIG. 4 shoWs tWo-photon upconverted ?uorescence emis sion spectra of ?uorine 1 at several fs pulsed pump Wave lengths (2.5><l0_4 M, ACN).

FIG. 5 shoWs the plot of the total integrated ?uorescence intensity of ?uorine 1 as a function of pump poWer at tWo fs pump Wavelengths.

FIG. 6 shoWs photoacid generation and time-dependent absorption spectra of PAG.

FIG. 7 shoWs time-dependent absorption and ?uorescence spectra of PAG and dye containing polymer in solution.

FIG. 8 displays a diagram of image formation Within a photosensitive polymeric ?lm containing PAG, and acid-sen sitive ?uorophore, alloWing tWo-photon induced, dual-chan nel ?uorescence imaging.

FIG. 9 shoWs tWo-photon ?uorescent images of photosen sitive ?lms developed (via 350 nm broadband exposure, 4.4 mW/cm2) using an Air Force resolution target mask. Image recorded by channel 1 at various exposure times. Data readout as a function of exposure time determined from ?uorescence

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4 intensity by scanning an xy line across one set of three member elements (yelloW line across set 5).

FIG. 10 shoWs tWo-photon ?uorescent images of photo sensitive ?lms developed (via 350 nm broadband exposure, 4.4 mW/cm2) using an Air Force resolution target mask. Image recorded by channel 2 at various exposure times. Data readout as a function of exposure time determined from ?uo rescence intensity by scanning an xy line across one set of three-member elements (yelloW line across set 5).

FIG. 11 shoWs tWo-photon ?uorescent images of photo sensitive ?lms developed (via 350 nm broadband exposure, 4.4 mW/cm2) using an Air Force resolution target mask. (a) Image recorded by channel 1, (b) image recorded by channel 2, and (c) ?uorescence intensity by scanning an xy line across one set of three-member elements (yelloW line across set 5) clearly shoWs the reverse parity of the signals.

FIG. 12 shoWs image formation (upon photoacid genera tion) Within photosensitive polymer ?lms for assembly of multi-layered structures. TWo-photon ?uorescence LSCM imaging using fs pulsed near-IR pump alloWs for 3-D volu metric imaging of the layered structure.

FIG. 13 shoWs (a) tWo-photon ?uorescent images of multi layered ?lms developed via 350 nm: broadband irradiation (6.0 mW/cm2) by exposure through TEM hexagonal and square grid masks. Fluorescence intensity plots for a line scan across a region (as de?ned by the yelloW line across the image area) provides (b) image readout in one layer, and (c) chang ing the depth (Z position) for image (signal) readout in the loWer layer Within a multi-layered system.

FIG. 14 gives the structure of tWo photosensitive polymers. FIG. 15 shoWs absorption and ?uorescence emission spec

tra of polystyrene based photosensitive polymers With and Without PAG.

FIG. 16 shoWs tWo-photon upconverted ?uorescence emis sion spectra of polystyrene based photosensitive polymers, and demonstration of tWo-photon absorption via quadratic intensity dependence.

FIG. 17 shoWs single-photon and tWo-photon upconverted ?uorescence emission spectra of polyethylene based photo sensitive polymers.

FIG. 18 shoWs tWo-photon ?uorescence image of the exposed photosensitive polymer Without PAG (left), along With the ?uorescence intensity pro?le through the bulk (xyZ scan) of the ?lm.

FIG. 19 shoWs tWo-photon ?uorescence image of the exposed photosensitive polymer With PAG (left), along With the ?uorescence intensity pro?le through the bulk (xyZ scan) of the ?lm.

FIG. 20 shoWs tWo-photon ?uorescence image of the exposed photosensitive polymer Without and With PAG (left and right, respectively), along With the ?uorescence intensity data readout.

FIG. 21 shoWs tWo-photon ?uorescence image of the exposed photosensitive polymer Without and With PAG (top and bottom, respectively), along With the 3-D ?uorescence intensity data readout.

FIG. 22 demonstrates tWo-photon Writing and readout in photosensitive polymer.

FIG. 23 shoWs a schematic diagram of tWo-photon Writing and recording system.

US 7,524,611 B2 5

DESCRIPTION OF THE PREFERRED EMBODIMENT

Thus, in a ?rst embodiment, the present invention provides a photosensitive composition comprising: 5

(a) a ?uorophore compound of Formula I:

Wherein X is selected from the group: iNHz, iNH(Cl-C6 alkyl), iN(Cl-C6 alkyl)2, iNH

(aryl), iN(aryl)2, iNHCO(Cl-C4 alkyl), 2-thiaZolyl substituted With 0-2 R2; 2-oXaZolyl substituted With 0-2 R2; 2-benZothiaZolyl substituted With 0-4 R2;

2-benZoXaZolyl substituted With 0-4 R2; and 2- or 4-pyridyl substituted With 0-4 R2, and N-carbaZolyl substituted With 0-4 R2;

Y is substituted With 0-5 R1 and is selected from the group: 20

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W is O, S, NH or N(Cl-C6 alkyl); Z is H, X, CN, iN:C:S, N02, iNH(C:S)iO(Cl C6 alkyl), iNH(C:S)iNH(Cl-C6 alkyl), iNH (C:$)*N(C1-C6 alkyl)» *P(:O)(OH)2, *P(:O) (OHXOici-ctr, alkyl), *P(:O)(O%1-C6 alkyl)» iN-succinimidyl, C1 -C20 alkyl substituted With 0-5 R1, Cl-C2O alkenyl substituted With 0-5 R1, Cl-C2O alkynyl

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6 substituted With 0-5 R1, C6-Cl4 aryl substituted With 0-5 R1, or 5-14 membered heterocycle substituted With 0-5 R1;

U and V, at each occurrence, are independently a bond, 4CH:CHi, 4CH:CH-phenylene-, or -phenylene CH:CHi;

R1 is independently amino, hydroxy, halogen, C l-C6 alkoxy, Cl-Cl0 alkyl, Cl-C6 haloalkyl, SH, SCH3, iNH (Cl-C6 alkyl), iN(Cl-C6 alkyl)2, iNH(aryl), iN(aryl)2, iNHCO(Cl-C4 alkyl), iN:C:S, iNH (C:S)A)(Cl-C6 alkyl), iNH(C:S)iNH(Cl-C6 alkyl), or iNH(C:S)iN(Cl-C6 alkyl)2;

R2 is independently amino, hydroxy, halogen, C l-C6 alkoxy, Cl-Cl0 alkyl, Cl-C6 haloalkyl, SH, SCH3, iNH (Cl-C6 alkyl), iN(Cl-C6 alkyl)2, iNH(aryl), iN(aryl)2, iNHCO(Cl-C4 alkyl), iN:C:S, iNH (C:S)A)(Cl-C6 alkyl), iNH(C:S)iNH(Cl-C6 alkyl), iNH(C:S)iN(Cl-C6 alkyl)2, iCOZH, or 4CO2(C1-C6 alkyl); and

R3 and R4, at each occurrence, are independently Cl-Cl6 alkyl, C 1% l0 haloalkyl, i(CH2)l_9CO2H, i(CH2)l_9 CO2(Cl-C6 alkyl), i(CH2CH2O)l_6H, or i(CH2CH2O)l—6(Cl_C6 alkyl);

(b) a photoacid generator; and (c) a polymer binder. In another embodiment, the present invention provides a

photosensitive composition comprising: (a) a ?uorophore compound of Formula I:

Wherein X is selected from the group: iNHZ, iNH(phenyl), iN(phenyl)2, 2-thiaZolyl substi

tuted With 0-2 R2; 2-oxaZolyl substituted With 0-2 R2; 2-benZothiaZolyl substituted With 0-4 R2; 2-benZoX aZolyl substituted With 0-4 R2; 2- or 4-pyridyl substi tuted With 0-4 R2, and N-carbaZolyl substituted With 0-4 R2;

Y is substituted With 0-2 R1 and is selected from the group:

R3

Z is H, X, CN, iN:C:S, N02, iNH(C:S)iO(Cl C6 alkyl), iNH(C:S)iNH(Cl-C6 alkyl), iNH (C:s)-N(c1-C6 alkynz, -P(:0)<0H)2, -P<:O) (OHXOici-ctr, alkyl), *P(:O)(O%1-C6 alkyl)» iN- succinimidyl, C 1 -C 1 0 alkyl substituted With 0-5 R1, Cl-Cl0 alkenyl substituted With 0-5 R1, Cl-Cl0 alkynyl substituted With 0-5 R1, phenyl substituted With 0-5 R1,

US 7,524,611 B2 7

naphthyl substituted With 0-5 R1, or 5-12 membered heterocycle substituted With 0-5 R1; said heterocycle is selected from the group: pyridyl, pyrimidinyl, furanyl, thiaZolyl, thienyl, pyrrolyl, imidaZolyl, benZofuranyl, benZothiophenyl, benZoXaZolyl, benZothiaZolyl, indolyl, indolenyl, isoxaZolinyl, quinolinyl, isoquinoli nyl, benZimidaZolyl, piperidinyl, pyrrolidinyl, triaZinyl, chromenyl, Xanthenyl, isothiaZolyl, isoXaZolyl, oXaZolyl, isoindolyl, carbaZolyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, morpholinyl, 1,4-benZoXaZinyl;


R1 is independently hydroxy, F, Cl, Br, I, Cl-C6 alkoxy, Cl-Cl0 alkyl, or Cl-C4 haloalkyl;

R2 is independently amino, hydroxy, F, Cl, Br, I, Cl-C6 alkoxy, Cl-Cl0 alkyl, Cl-C6 haloalkyl, SH, SCH3, iNH (C1-C6 alkyl), *MCI-QI, alkynz, *Nmaryn, iN(aryl)2, iNHCO(Cl-C4 alkyl), %O2H, or iCOz (C l-C6 alkyl); and

R3 and R4, at each occurrence, are independently Cl-Cl6 alkyl, Cl-C1O haloalkyl, i(CH2)l_9CO2H, i(CH2)l_9 CO2(C1-C6 alkyl), i(CH2CH2O)l_6H, or i(CH2CH2O)l-6(Cl_C6 alkyl);

(b) a photoacid generator; and (c) a polymer binder. In another embodiment, the present invention provides a

photosensitive composition comprising: (a) a ?uorophore compound of Formula I:

XiUiYiViZ I

Wherein Y is

R3

and substituted With 0-2 R1; (b) a photoacid generator; and (c) a polymer binder. In another embodiment, the present invention provides a

photosensitive (polymer) composition, Wherein the photo acid generator is selected from the group consisting of diphe nyl iodonium hexa?uorophosphate, diphenyl iodonium hexa?uoroarsenate, diphenyl iodonium hexa?uoroanti monate, diphenyl p-methoxyphenyl iodonium tri?ate, diphe nyl p-toluenyl iodonium tri?ate, diphenyl p-isobutylphenyl iodonium tri?ate, diphenyl p-tert-butylphenyl iodonium tri ?ate, triphenylsulfonium hexa?uorophosphate, triphenylsul fonium hexa?uoroarsenate, triphenylsulfonium hexa?uoro antimonate, triphenylsulfonium tri?ate, dibutylnaphthylsulfonium tri?ate and mixture thereof.

In another embodiment, the present invention provides a photosensitive composition, Wherein the polymer binder is selected from the group: polystryene and its derivatives, poly acrylates, polymethacrylates, polycarbonates, polyurethanes, polysiloxanes, nylons, and polyesters.

In another embodiment, the present invention provides a photosensitive polymer composition comprising:

20

30

35

40

45

50

55

60

65

8 (a) a ?uorophore-containing polymer comprising a unit

selected from:

Wherein X is selected from the group:

iNHZ, iNH(Cl-C6 alkyl), iN(Cl-C6 alkyl)2, iNH (aryl), iN(aryl)2, iNHCO(Cl-C4 alkyl), 2-thiaZolyl substituted With 0-2 R2; 2-oxaZolyl substituted With 0-2 R2; 2-benZothiaZolyl substituted With 0-4 R2;

2-benZoXaZolyl substituted With 0-4 R2; and 2- or 4-pyridyl substituted With 0-4 R2, and N-carbaZolyl substituted With 0-4 R2;


US 7,524,611 B2 9

W is O, S, NH or N(Cl-C6 alkyl);


n is 1-50;

A is O or S;

B is 0 or NH;

is independently atnino, hydroxy, halogen, C l-C6 alkoxy, Cl-Cl0 alkyl, Cl-C6 haloalkyl, SH, SCH3, iNH

iN(aryl)2, iNHCO(Cl-C4 alkyl), -N:C:S, iNH

alkyl), or iNH(C:S)iN(Cl-C6 alkyl)2; R2 is amino, hydroxy, halogen, C l-C6 alkoxy, C 1 -C10 alkyl,

Cl-C6 haloalkyl, SH, SCH3, iNH(Cl-C6 alkyl), iN(Cl-C6 alkyl)2, iNH(aryl), iN(aryl)2, iNHCO (Cl-C4 alkyl), -N:C:S, iNH(C:S)A)(Cl-C6 alkyl), iNH(C:S)iNH(Cl-C6 alkyl), iNH (C:S)iN(Cl-C6 alkyl)2, iCOZH, or iCO2(Cl-C6 alkyl); and

R3 and R4, at each occurrence, are independently Cl-Cl6 alkyl, Cl-Cl0 haloalkyl, i(CH2)l_9CO2H, i(CH2)l_9 CO2(Cl-C6 alkyl), i(CH2CH2O)l_6H, i(CH2CH2O)l-6(Cl_C6 alkyl);

and optionally (b) a photoacid generator.

In another embodiment, the present invention provides a photosensitive polymer composition, comprising:

(a) a ?uorophore-containing polymer comprising a unit selected from:


iNHZ, iNH(phenyl), iN(phenyl)2, 2-thiaZolyl substi tuted With 0-2 R2; 2-oxaZolyl substituted With 0-2 R2; 2-ben ZothiaZolyl substituted With 0-4 R2; 2-benZoXaZolyl substi tuted With 0-4 R2; 2- or 4-pyridyl substituted With 0-4 R2, and N-carbaZolyl substituted With 0-4 R2;

01

20

25

30

35

40

45

50

55

60

65

10 Y is substituted With 0-2 R1 and is selected from the group:

R3


n is 1-20; R1 is independently hydroxy, F, Cl, Br, I, Cl-C6 alkoxy,

Cl-Cl0 alkyl, or Cl-C4 haloalkyl; R2 is independently amino, hydroxy, F, Cl, Br, I, Cl-C6

alkoxy, Cl-Cl0 alkyl, Cl-C6 haloalkyl, SH, SCH3, iNH (Cl-C6 alkyl), iN(Cl-C6 alkyl)2, iNH(aryl), iN(aryl)2, iNHCO(Cl-C4 alkyl), iCOZH, or iCOz (C l-C6 alkyl); and

R3 and R4, at each occurrence, are independently Cl-Cl6 alkyl, Cl-C1O haloalkyl, i(CH2)l_9CO2H, i(CH2)l_9 CO2(Cl-C6 alkyl), i(CH2CH2O)l_6H, or i(CH2CH2O)l—6(Cl_C6 alkyl);

and optionally (b) a photoacid generator. In another embodiment, the present invention provides a

photosensitive composition comprising: (a) a ?uorophore-containing polymer comprising a unit

selected from:

O O

Wherein Y is

US 7,524,611 B2 11 12

and substituted With 0-2 R1; In another embodiment, the present invention provides a

and Optionally (b) a photoacid generator‘ photosens1t1ve polymer compos1t1on, comprising: (a) a ?uorophore-containing polymer comprising a unit In another embodiment, the present invention provides a _ _

WheremY 1s photosensitive polymer composition comprising: (a) a ?uorophore-containing polymer comprising a unit

selected from:


iNRS, and 15

and substituted With 0-2 R1;

and (b) a photoacid generator. R6

In another embodiment, the present invention provides a /N S 20 novel compound of Formula II:

/ , S N

R7 25


R3 30

R4


iNHZ, iNH(aryl), iN(aryl)2, 2-benZothiaZolyl substi 35 tuted With 0-4 R2;

2-benZoXaZolyl substituted With 0-4 R2; and 2- or 4-pyridyl substituted With 0-4 R2, and N-carbaZolyl substituted

\ With 0-4 R2;

45 Cl-C2O alkenyl substituted With 0-5 R1, Cl-C2O alkynyl m is 1-50; substituted With 0-5 R1, C6-Cl4 aryl substituted With 0-5 R1 is independently amino, hydroxya halogen, Cl_C6 R1, or 5-14 membered heterocycle substituted With 0-5

alkoxy, cl-cl0 alkyl, C1-C6 haloalkyl, SH, SCH3, iNH R1; (C1-C6 alkyl), iN(C1_C6 a1ky1)2, *NHQII'YD, 50 U and V, at each occurrence, are independently a bond, *N(a1'y1)2, *NHCO(C1'C4 alkyD: *NICIS, *NH 4CH:CHi, 4CH:CH-phenylene-, or -phenylene (C:s)w(C1-C6 alkyl), -NH(C:s)-NH(C1-C6 CHICHi, aIkyD’Or iNH(C:S)iN(C1_C6 a1kyD2; R1 is independently amino, hydroxy, halogen, Cl-C6

R3 and R4, at each occurrence, are independently Cl-Cl6 alkox C _C alkyl C _C haloalkyl SH SCH iNH alkyl, cl-cl0 haloalkyl, i(CH2)l 9CO2H, i(CH2)l 9 55 y’ 1 1° ’ 1 6 ’ ’ 3’

2 1 6 y 2 2 2 1-6 2 iN(ary1)2,*NHCO(C1-C4a1ky1),iN:C:S,iNH

C6-Cl4 aryl substituted With 0-5 R1, or 5-14 membered 60 R2 is independently amino: hydroxy, halogen, C1-C6 heterocycle substituted With 0-5 R1; alkoXy, C l-C 10 alkyl, C l-C6 haloalkyl, SH, SCH3, iNH

R6 and R7 at each occurrence, are independently H, Cl-Cl- (Cl-C6 alkyl): *N(C1'C6 alkyl)» *NHQII'YI), C16 alkyl, Cl-Cl0 haloalkyl, i(CH2)l_9CO2H, *N(aryl)2,iNHCO(Cl-C4alkyl),iN:C:S,iNH i(CH2)l_9CO2(Cl-C6 alkyl), i(CH2CH2O)l_6H, or 65 (C:S)A)(Cl-C6 alkyl), iNH(C:S)iNH(Cl-C6 *(CH2CH2O)1.6(C1-C6alkyl); alkyl), iNH(C:S)iN(Cl-C6 alkyl)2, icozn, or

and (b) a photoacid generator. 4CO2(C1-C6 alkyl); and

(12) united states patent (10) patent no.: us 7,524,611 b2 ... · us. patent apr. 28,2009 sheet 2...

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