Program: Center for Optical Sensors and Spectroscopies...

http://http://www.coss.phy.uab.eduwww.coss.phy.uab.edu//Center for Optical Sciences and Center for Optical Sciences and SpectroscopiesSpectroscopies

Program: Center for Optical Program: Center for Optical Sensors and Sensors and SpectroscopiesSpectroscopies (COSS)(COSS)

Prepared by Dr. Chris Lawson (COSS Director, UAB)Dr. Sergey Mirov (COSS co-Director, UAB)Dr. Robert Pitt (co-PI, UA)Dr. Richard Fork (co-PI, UAH)Prepared forAlabama EPSCoR Annual Meeting, March 28-29, 2005


UAB

UAHUA

COSS is a multi-institutional center(consisting of researchers and facilities from UAB, UA, and UAH)

COSS VISION The COSS center will be recognized nationally for excellence in lasers, optical sensors and spectroscopy addressing both education and research on environmental, biomedical, and

national security issues.

Laser-enabled optical sensor and spectroscopic technologies has had a significant impact all over the world on the major institutions in health care, biomedicine, communications, materials characterization and processing, defense, aerospace, environmental health, and national security, and this trend can only be expected to accelerate in the future.

COSS MISSIONCOSS MISSION

The mission of the COSS is to promote optical sensing and spectroscopy research on environmental, biomedical, and national security issues through collaborative use of resources and expertise among the member universities, government and industrial laboratories, and improve sensor techniques using recently developed revolutionary laser and spectroscopic technologies.


The objective of the COSS is to utilize optical sensor technology used for detecting environmental contaminants and to improve these techniques using recently developed revolutionary laser and spectroscopic technologies.

One application will be Counter-Terrorism related applications such as the detection of chemical warfare agents and their precursors, explosive agents, and biological warfare agents

This capability will help to detect dangerous agents at the earliest possible stage (e.g., airport screening) before deployment by terrorists, and may avoid future chemical, biological, or radioactive terrorist attacks. This project could save thousands of lives.

Another application is to assist in emergency response to protect human health after natural disasters through the rapid detection of organic and inorganic toxicants.

The recent problems emphasized by Hurricane Katrina show that a rapid and efficient method to detect organic and inorganic toxicants in sediments and waters would be a very important tool to protect the public health of rescue workers and those responsible for rebuilding the devastated areas

What is the Purpose of the Center for Optical Sensors and Spectroscopies (COSS)?


•areas

How optical spectroscopic sensing of toxins works. optical nose dog nose

Sniff. Automated intake sampling. Molecules above the solution are delivered into optical cell

Sensor-odor molecules interaction

Tunable laser radiation excites molecules in the cell

Inhaled volatiles are introduced to array of broadly specific receptor molecules

Signal Generation

Interaction of light with molecules gives rise to characteristic absorption spectra

Molecule-receptor binding generates series of action-potential patterns

Signal recognition

Potential patterns are relayed to the various layers of the olfactory bulb and these are passed on to higher level brain regions for identification

Smells like coffee

Odor identification

Absorption spectra are fed into a computer based spectrum recognition algorithm

Molecules identification and quantification

Sensitivity of the optical nose depends on linewidth, stability, and power of the pump laser, spectroscopic detection platform and noise reduction techniques and can be as good as sup-

parts per trillion, more than 100 times better than sensitivity of a dog nose.


• The proposed Center, consisting of researchers from UAB, UA, and UAH will utilize current research strengths in Alabama, and combine them in a unique way to provide a completely new high technology capability for the state, and the development of shared research facilities that will provide crucial critical mass and infrastructure.

• One primary focus of the shared facilities is the upgrade of a multi-purpose facility for development of new optical spectroscopy laser sources

• Another focus will be centered around the purchase of a unique multipurpose COSS Cluster Spectroscopy System for ultra-sensitive detection of toxic materials, consisting of a confocal microscope system for Raman and photoluminescence spectroscopy, integrated with near field optical/atomic force microscopy system.

• In addition to the inherent capabilities of this system, a primary research focus on this proposal will be to increase its performance even further with a new ultra-fast CCD detection system, and by upgrading the laser sources with recently patented COSS Center laser technology.

COSS SHARED CORE FACILITIES


UAB

UAH UA

GOAL 1: To create the infrastructure (core

spectroscopic research facility) for the collaborative

use of core facilities and specialized expertise in novel laser sources and

sensing of organic, inorganic and toxic agents.

GOAL 2: To foster important partnerships among research universities, national labs and industry of Alabama and nationwide.

GOAL 3: To strengthen research and graduate programs and human infrastructure at UAB, UA, and UAH.

GOAL 4: To Promote Minority/Under-

Represented Group Participation in COSS-Related Research and

Education

GOAL 5: To provide educational outreach for K12 students and teachers.GOAL 6: To effectively

manage and coordinate the COSS center

GOAL 7: To develop and characterize novel active and passive materials and light sources relevant for laser sensing, spectroscopic detection of organic, inorganic and toxic agents and counter-terrorism applications.

GOALS MILESTONES


PROGRAM PLAN: 1. Upgrade Nd:YAG laser with optical parametric oscillator2. Upgrade DILOR XY microRaman system with NSOM/AFM option3. Upgrade DILOR XY microRaman system with ultrafast gated (80 ps) CCD camera (ICCD)PAYOFF: The upgraded system will provide us a unique capability for on-site, nondestructive

detection and characterization of explosives and biological, chemical and toxic substances.

Nd:YAG laser will be upgraded with the optical

parametric oscillator tunable over 0.4-2.7 µm

spectral range

Dilor XY microRaman System

Combining microRaman and FLIBS spectroscopy.Comparison of femtosecond produced plasma emission lines (left) or aluminum film and those obtained from a nanosecond formed plasma (right). The broad background emission is not present in the femtosecond case. This makes the detection of chemical and biological agents at low concentrations easier since the peaks come directly out of the baseline.

Combining scanning probe and Raman spectroscopy. Now Raman data can be recorded and correlated with high spatial resolution topographic, electrical, thermal and near-field optical data.

Goal 1:Goal 1: To create the infrastructure (core spectroscopic research facility) for the collaborative use of core facilities and specialized expertise in

novel laser sources and sensing of organic, inorganic and toxic agents.


PROGRAM PLAN: To undertake joint university-industry, University –national or international labs projects

IndustryNational Labs

&Local centers

UAB

UAH UA

COSS Other EPSCoR Centers

International Collaboration

Goal 2:Goal 2: To foster important partnerships among research universities, national labs and industry of Alabama and nationwide

•Center for Environmental Cellular and Signal Transduction (CECST)

•Alabama Center for NanoTechnology Materials (ACNM)

•Extended Alabama Structural Biology Consortium (EASBC)


Goal 2:Goal 2: To foster important partnerships among research universities, national labs and industry of Alabama, and nationwide.

Ion ImplantationManufacture p-n junctions in ZnSe

Quantum Dot formation

Color Center formation (Auburn Nuclear Center)

Our Goals

Produce first electrically pumped RT, broadly tunable Mid-IR laser

Produce new quantum dot based Cr2+:ZnS and Cr2+:ZnSe lasers

Laser Crystal Preparation

Collaboration

ACNM


Goal 2:Goal 2: To foster important partnerships among research universities, national labs and industry of Alabama, and nationwide.

EASBC/CBSE

Design Space Grade Optical Nose

Design and Analysis Tools

Engineer pathogen selective antibodies for “Sensing through the walls”

COSS

Characterize protein crystal quality with MicroRaman facility.

Build laser spectrometer for optical nose.

“Sensing through the walls” novel methods of selective excitation and detection through walls of signals from nanowires attached to pathogens.

Collaboration


Goal 3:Goal 3: To strengthen research and graduate programs and human infrastructure at UAB, UA, and UAH.

Recruit new faculty and outstanding graduate students :

two research assistant professors at UAB

faculty member with expertise in biosensors (UAB)

faculty with expertise in urban infrastructure

Advertise UAB, UAH and UA graduate programs in lasers, spectroscopy and environmental science nationally

Offer specialized and advanced courses to graduate students :

Two semester series in Laser Physics, Laser Spectroscopy, nanomaterialsWorkshops, in Stormwater management, Construction site erosion control, International urban water infrastructured, Effects and fates of hazardous materials


Goal 3:Goal 3: To strengthen research and graduate programs and human infrastructure at UAB, UA, and UAH

Obtain non-EPSCoR funding

1. NSF impurity doped quantum confined II-VI structures for electrical pumping of mid-IR lasers –funded

2. NSF Laser optical nose - funded3. NIH, early optical nose diagnostics of lung cancer - submitted4. DARPA, sensing biological pathogens through the wall - submitted5. ARL proposal for sensor protection - submitted6. NIH proposal on Imaging guided interventions - submitted7. NSF proposal on environmental sampling after natural disasters8. EPA proposal on small community water quality monitoring efforts9. NIH proposal on international environmental health education

initiatives10. Research and royalty Agreements with Industrial Collaborators and

financing through Venture Capitalists.


Lawrence Luke summer 2005 REU program. Studied novel mid-IR laser materials at COSSPROGRAM PLAN:

1. Implement NSF-funded REU (UAB physics) at COSS 2. Implement Bridge for Doctorate program at UAB and UAH3. Implement EMAP minority summer program at UA

COSS center takes part in the EPSCoR/LSAMP summer research conference, July 22, 2005.

New UAB physics graduate fellow Ms. Hadiyah Green sponsored by UAB Bridge for Doctorate Program with her mentor Dr. S.Mirov, COSS Co-Director

Goal 4:Goal 4: To Promote Minority/Under-Represented Group Participation in COSS-Related Research and Education

Ms. Clarissa Byrd presents a talk on Optical Detection of Atmospheric Contaminants. Mentor –Dr. R.Fork, UAH COSS member


Goal 5:Goal 5: To provide educational outreach for K12 students and teachers.

NSF- Research Experiences for Teachers

•Recruit high school teachers for training at COSS via NSF-funded RET program (UAB physics).

•Coordinate educational outreach at schools with Science in Motion Program (UAB) at UAB and UAH.•Develop new experiments for science in motion program.


PROGRAM PLAN: 1. Provide effective oversight of the COSS center

1. Hold yearly meetings with the external advisory board committee2. Hold quarterly management meetings (meetings or teleconferences)3. Submit quarterly reports to the Alabama EPSCoR 4. Hold periodic scientific meetings or teleconferences for co-investigators5. Monthly budget reviews

2. Monitor individual project/task status through quarterly status reports and website3. To inform general public and EPSCoR Office on COSS activities through website, press releases

UAB

UAH

UA

Alabama EPSCoR Steering CommitteeAlabama EPSCoR

Steering Committee

Goal 6:Goal 6: To effectively manage and coordinate the COSS center

Advisory Board Committee


Goal 7:Goal 7: To develop and characterize novel active and passive materials aTo develop and characterize novel active and passive materials and light nd light sources relevant for laser sensing, spectroscopic detection of osources relevant for laser sensing, spectroscopic detection of organic, inorganic rganic, inorganic

and toxic agents and counterand toxic agents and counter--terrorism applicationsterrorism applications.

I. Development and characterization of novel active and passive optical materials for optical sensor technology

II. Development of light sources relevant to spectroscopic applications

III. Development of laser spectroscopic systems for detecting environmental contaminants and Counter-Terrorism related applications


I.I. Development and characterization of novel active and passive optical materials for optical sensor technology

Development of II-VI laser materials Diffusion doping of TM ionsLaser Ceramic MaterialsQuantum dot and quantum well laser structuresThin Film Preparation and Characterization

Pay off: Fabrication of the first electrically pumped RT, broadly tunable Mid-IR laser

ZnS

Si

ZnS

Si

5 µm

ZnS

CBA


II. Development of light sources relevant to spectroscopic applications

Compact fiber laser pumped Er:YAG and Ho:YAG lasersRoom temperature lasers tunable in MIR spectral region

Pay off: Development of heat-seeking missile countermeasures. Lasers for Mid-IR sensing.


I. Development and characterization of novel active and passive optical materials for optical sensor technology Development of II-VI laser materials by diffusion doping of TM ions

Crystals were synthesized by Crystals were synthesized by CVT using iodine as transport CVT using iodine as transport agent ( C(Iagent ( C(I22)=2)=2--5 mg/cm5 mg/cm3 3 ))Ampoule size: Ampoule size: ∅∅20mm x 20mm x 200mm200mmTemperature range 1200Temperature range 1200ooC C --11001100ooCC

P=10P=10--55 torr torr T= 1000 C T= 1000 C t=7t=7--20 days20 days

Pulsed laser Pulsed laser depositiondeposition

Thermal annealingThermal annealing

The polished samples of The polished samples of 11--2 mm thickness and up 2 mm thickness and up to 5 mm in aperture were to 5 mm in aperture were used for spectroscopic used for spectroscopic and laser measurementsand laser measurements

Chromium thin Chromium thin film deposition film deposition on the crystals on the crystals wafer by means wafer by means of pulsed laser of pulsed laser deposition deposition methodmethod

Chemical Vapor Chemical Vapor Transport (CVT)Transport (CVT)

Crystal

PowderCr

Crystal

Crystalλ=532 nm

E=500 mJZnS+I2↔ ZnI2+1/2S2

Mirov, Fedorov, US Patent 6,940,486 November 2005



Novel Co:ZnS passive bulk material

Saturation at 731nm

Photon Flux(mJ/cm2)

0 100 200 300 400 500 600 700 800

Tran

smis

sion

0.0

0.2

0.4

0.6

0.8

1.0

Q-Switch

time, us

0 20 40 60 80 100

V

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Lamp

Alexandrite crystalFilter Liot

Rout=50% R=100%

Power Meter

Oscilloscope

Wavemeter

Photodiode

ZnS:Co:Cr

time, ns0 50 100 150 200 250 300 350 400

0

1

2

Q-switching of alexandrite laser was achieved with ZnS:Co:Cr at 754nm with a pulse duration of approximately 50 ns and 15mJ of energy.

R.A.Sims, et al, Photonics West 2006.



Development of II-VI ceramic laser materials

A fabrication process of optical material based on hot-pressed Cr2+:ZnSe ceramic with optical quality sufficient for the first everdemonstration of gain-switched lasing in such a material was made.

ZnSe+ CrSe(0.1-0.01%)

ZnSe

P=60MPa

ZnSe+ CrSe(1%) ∅15 mm

P=30-350MPa

CLEO’05



Development of II-VI ceramic laser materials

The laser yielded 2 mJ of output energy at a slope efficiency up to 5%. Further investigations are needed for developing of hot-pressed samples with high optical density (αmax=5-10 cm-1 at 1.8 µm) and low losses. The presented results demonstrate the first proof of the feasibility of the mid-IR laser systems based on hot-pressed ceramic. Further technological advances are needed to decrease the passive loss of hot-pressed ceramics to achieve large impact factors of ceramics on the synthesis of large-scale mid-IR laser media.

Abs. Energy (mJ)0 10 20 30 40 50 60

Out

put E

nerg

y (m

J)

0

1

2

BCA

η=3%η=5%η=8%

CLEO’05



Development of II-VI thin film laser materials

SEM surface (C) and cross section (A,B) images of Cr doped ZnS thin film with thickness 12 µm and cross section (B,C) and 200 nm ZnS thin films (A)

Schematic of integrated PLD facility

µs4 6 8

Sig

nal (

a.u.

)

0.1

1

AThin Film

Bulk

300K

20K23K

300K

Luminescence life time measurements of bulk and thin film samples at 300K and ~20K.

Face

Edge

Bulk

Constructive InterferenceDestructive Interference

Plots of the luminescence spectra of a thin film sample in different geometries and a bulk sample for comparison.



Mid-IR Luminescence of ZnS nanoparticles

A

Wavelength, nm2500 3000 3500 4000 4500 5000

0

2

4

6

8

10

12

14

B

time, µs

0 50 100 150 200

Intensity, a.u.

0.01

0.1

Mid-IR photoluminescence spectra of chromium doped annealed ZnS nanoparticles; B- Kinetics of fluorescence measured at 2-5 µm spectral range


I. Development and characterization of novel active and passive optical materials for optical sensor technology Novel TM:II-VI materials

1.The first Co:ZnSe passive Q-switch was developed for 745nm. (Photonics West 2006)

2.The first hot pressed Cr:ZnSe samples showed gain switched lasing (CLEO 2005)• These results as well as the continuing research in TM:ZnSe materials allow us to

continue leading the field in solid state photonics research.

We developed techniques for providing thermal diffusion for variWe developed techniques for providing thermal diffusion for various transition metal doping in IIous transition metal doping in II--VI VI materials.materials.

We are developing techniques to produce PLD grown thin films of We are developing techniques to produce PLD grown thin films of ZnSe doped with Chromium for ZnSe doped with Chromium for future research in electrically pumped future research in electrically pumped pp--nn junction based laser systems.junction based laser systems.

We are developing techniques to produce solWe are developing techniques to produce sol--gel grown quantum dots of ZnSe doped with gel grown quantum dots of ZnSe doped with ChromiumChromium

1. A. Gallian, V. V. Fedorov, S. B. Mirov, V. V. Badikov, S. N. Galkin, E. F. Voronkin, A. I. Lalayants, “Hot-Pressed Ceramic Cr2+:ZnSe Gain- Switched Laser”, CLEO, Baltimore, Maryland, May 22-27 2005

2. A. Gallian, V. V. Fedorov, J. Kernal, J. Allman, S. Mirov, E. M. Dianov, A. O. Zabezhaylov, I. P. Kazakov “En Route to Electrically Pumpable Cr2+ Doped II-VI Semiconductor Lasers” , ASSP, Vienna, Austria, Feb 6-9 2005

3. A.R. Gallian, V.V. Fedorov, J. Kernal, J. Allman, S.B. Mirov, E. Dianov, A. Zabezhaylov, I. Kazakov“Photoluminescence studies of MBE grown thin films and bulk Cr:ZnSe”, SESAPS, Oakridge, TN, Nov 11-13 2004

time, ns0 50 100 150 200 250 300 350 400

0

1

2

Co:ZnSe Q-Switch

Ceramic Cr:ZnSe


II. Development of light sources relevant to spectroscopic applications.

Tm fiber laser pumped Ho:YAG laser

Output power of CW and 10kHz Q-switched Ho:YAG laser vs pump power.

CW and 10 kHz Q-switched with 50% OC

Pump power, W2 4 6 8 10 12 14 16 18 20 22 24

Out

put p

ower

, W

0

2

4

6

8

10CW QS, 10 kHz

The maximum achieved output energy was 15 mJ at 100Hz repletion rate with sustained damage free operation of the laser. Experiments show that at 25 W of pump power up to 25 mJ of output energy is achievable.

The Ho:YAG laser operated in the Q-switched regime at 50 Hz-10 kHz repetition rates. The minimum pulse duration was 17 ns at 100 Hz and increased to 20 ns at repetition rate of 1000 Hz.

ASSP’06


Lasing of Cr2+:ZnSe via Ionization Transitions (ASSP’05)

µs0 2 4 6 8

mV

0

5

10

15

20

25

0 2 4

Pump Pulse

Lasing from 532nm pumping


µs

Build up time


Pump Energy, mJ5 10 15

Lasi

ng In

tens

ity, a

b.un

.

0

5

10

15

20

25

wavelength, nm1800 2000 2200 2400 2600 2800 30000

1

Inte

nsity

, ab.

un.


Luminescence from 532nm pumping

Lasing and Luminescence spectrum under 532nm excitation

Lasing output

intensity

versus pump

energy

ZnSe CB

VB

Eac

Ed

Cr2+/Cr+

Time+ +

hνpump

hνos

Cr2+*

5E

5T2

Cr2+*


Mid-IR Electroluminescence of n-Cr:ZnSe (ASSP’06 WB21)Absorption Spectra Al:Cr:ZnSe

K (cm

-1)

0

2

4

6

8

Wavelength (nm)1200 1600 1800 2000

I-V Curves for Cr-Al:ZnSe Samples # 1 & 2

Voltage(V)-80 -60 -40 -20 0 20 40 60 80

Cur

rent

(mA

)

-10-8-6-4-2

246810

Sample#2

Sample#10

~30KΩ

~7.5KΩ

Time (µs)-200 0

Vol

ts

-2

mid-IR optical signal

Electrical pulse

200

-4

Visible Luminescence ofVZn-Al complex

Inte

nsity

, a.u

.

mid-IR Cr2+ electroluminescence

Wavelength (nm)

Inte

nsity

, a.u

.

Wavelength (nm)400 600 800 1800 2200 2600

Cr2+ optical pumping


RT Fe:ZnSe Lasing in Nonselective cavityRT Fe:ZnSe Lasing in Nonselective cavity

B

Pump Energy, mJ/cm2

50 100 150

Sign

al, a

.u.

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4Ai - 40mJ/cm2

ii -110 mJ/cm2

iii-170 mJ/cm2

wavelength, nm

3750 4000 4250 4500 4750 5000

Sign

al, a

.u.

i

ii

iii

Emission spectra of Fe:ZnSe crystal versus pump density; B- Output of RT gain-switched Fe:ZnSe lasing in nonselective cavity versus pump

density


RT Fe:ZnSe Lasing in RT Fe:ZnSe Lasing in LittrowLittrow Cavity Cavity

wavelength, nm

3800 4000 4200 4400 4600 4800

Lase

r out

put ,

a.u

.

0.0

0.2

0.4

0.6

0.8

1.0

i

ii

Tuning curve of RT gain-switched Fe:ZnSe laser (i) and example of oscillation spectrum at 4490 nm (ii)


wavelength, nm3800 4000 4200 4400 4600 4800

Lase

r out

put ,

a.u

.

0.0

0.2

0.4

0.6

0.8

1.0

II. Development of light sources relevant to spectroscopic applications. Novel Mid-IR Tunable Lasers

B

wavelength, nm1600 1800 2000 2200 2400 2600 2800

Inte

nsity

, a.u

.

(II)(I)

We demonstrated, for the first time ever, an observation of lumiWe demonstrated, for the first time ever, an observation of luminescence under electrical nescence under electrical excitation from chromiumexcitation from chromium--doped ndoped n--type ZnSetype ZnSeWe developed high optical density and high quality Fe:ZnSe crystWe developed high optical density and high quality Fe:ZnSe crystals and demonstrate the als and demonstrate the feasibility of Fe:ZnSe crystals for gainfeasibility of Fe:ZnSe crystals for gain--switched lasing at room temperature (RT).switched lasing at room temperature (RT).We demonstrated the first room temperature gainWe demonstrated the first room temperature gain--switched tunable oscillation of Fe:ZnSe switched tunable oscillation of Fe:ZnSe crystal over 3.9crystal over 3.9--4.8 4.8 µµm spectral range.m spectral range.Ten reports, Ten reports, 12 articles/proceedings, one book chapter, and one patent12 articles/proceedings, one book chapter, and one patent have been have been students and researchers from the COSS center at UAB.students and researchers from the COSS center at UAB. One PhD dissertation has been One PhD dissertation has been successfully defended.successfully defended.

1. J. Kernal, V. V. Fedorov, A. Gallian, S. B. Mirov, and V. V. Badikov,"3.9-4.8 µm gain-switched lasing of Fe:ZnSe at room temperature“, Optics Express, V. 13, p. 10608, (2005)

2. Fedorov, J. Kernal, A. Gallian, S. B. Mirov, V. V. Badikov “3.9-4.8 µm gain-switched lasing of Fe:ZnSe at room temperature”, Photonics West Conference/ SOLID STATE LASERS XV [6100-13], (2006)

3. L. Luke, V. V. Fedorov, I. S. Moskalev, A. Gallian, S. B. Mirov, “Middle-infrared electroluminescence of n-type Cr doped ZnSe crystals, Photonics West Conference/ SOLID STATE LASERS XV [6100-26], (2006)

1) The first optically pumped chip-scale laser operating at room temperature in the window of atmospheric transparency over 3.9-4.8 um spectral range has been realized.

2) The first middle-infrared (2-3mm) electroluminescence of chromium doped ZnSe has been demonstrated.

Both results represent novel approach in laser physics - laser oscillation occurs under optical or electrical excitation due to electron transitions within the Cr and Fe impurity incorporated into semiconductor crystal.

This approach enables a new pathway for ultrasensitive miniature mid-IR sensors having significant technological relevance for: detection of explosives, chemical and biological warfare agents; industrial process control; biomedical applications, i.e. detecting markers associated with malignant tissues and measurement of medically important molecular compounds in the exhaled breath of patients; many other industrial and scientific applications.

IR lasing of Fe:ZnSe

Electroluminescence of Cr:ZnSe


Dilor XY microRaman System

There is a great need for:

•Minimization of sample preparation•Maintenance of high sensitivity•Nearly real-time results

Colloidal metallic nanoparticles prepared by laser ablation and MethophotonicsKlariteTM SERS substrate

SERS spectrum of PAHs challenging sample prepared by using traceable standard materials

Advantages of SERS:

• Minimal sample preparation required• High sensitivity to specific compounds• Real time measurements (less than afew minutes)

• Challenging multicomponent samplesanalysis

• Infield detection and characterization of environmental pollutants are possible

III. Develop laser system for detecting environmental contaminants Department of Physics at UAB and Department of Civil and Environmental Engineering at UA teams developing a new technique based on Surface Enhanced Raman Spectroscopy (SERS) for rapid identification of polycyclic aromatic hydrocarbons (PAHs), pesticides and herbicides pollutants


Researchers at UA Environmental Institute have prepared test samples and performance objectives for the new optical spectroscopic measurement instrumentation.

Challenge samples are being obtained and parallel tested to measure the actual performance of the laser instruments.


Absorption spectra of silver and gold colloidal metal nanoparticles prepared by laser ablation method.

Silver and gold colloidal metal nanoparticles prepared by laser ablation method.

Metal wire

Ar In Ar Out

Pulsed laser light

Schematic diagram of laser ablation method. Pulsed laser light is focused on silver or gold wire placed in double distilled water under continues degassing by argon.

The advantage of laser ablation is absence of chemical reagents in solutions comparing to other conventional method for preparing metal colloids. Therefore pure colloids are produced and being used in UAB Laser laboratory for surface enhanced Raman spectroscopy (SERS).

Various laser conditions such as wavelength, energy and pulse duration effect average particle size and shape, which can be adjusted in controllable manner.

Preparation of colloidal metal nanoparticles by laser ablation.


Core. Water n=1.33

Cladding. Teflon ® AF 2400 n=1.29

Laser light

10+ miters

To Raman spectrometer

The alternative approach is use of liquid waveguide capillary cell (LWCC). Capillary tube made of commercialavailable polymer Teflon-AF 2400 with refractive index 1.29 filled up with water acts as liquid core waveguidTeflon-AF 2400 is transparent in 200-2000nm spectral region therefore Vis light coupled into such a waveguidcould propagate to a significant distance. This will allow to increase weak Raman signal by several orders magnitude.

Liquid Waveguide Capillary Cell (LWCC).


5x10-3

4

3

2

1

Abs

orba

nce

440435430425420415Wavelength /nm

W aveleng th ,nm 1038 1039 1040 1041 1042

Opt

ical

Den

sity

505 510 515

Wavelength, nm505 510 515505 510 515

Inte

nsity

, arb

.un

0

10000

20000

30000

40000

50000

60000

70000RO water Distilled water Cu - 10 µg/l

CuCu

Cu

3ω (2

nd o

rder

)

3ω (2

nd o

rder

)

3ω (2

nd o

rder

)

Example of sensitive LAF detection of Cu atoms in water sample (Cu-10µg/L), distilled water, and deionized water

LensLens

SpectrographARC-750

CCD

PC

Sample(in graphite furnace)

HV Pulse GeneratorPG-200

Aperture

FiberGuide

Tunable UVlaser

LASER ATOMIC FLUORESCENCE SPECTROSCOPYPersistent photon-gated spectral hole burning in

LiF:F2- color center crystal

EVANESCENT CAVITY RING-DOWN SPECTROSCOPY (E-CRDS) OF HEMOGLOBIN

ABSORPTION

⎟⎠⎞

⎜⎝⎛∆

=20

rtAbsτττ

III. Develop laser system for detecting environmental contaminants and Counter-Terrorism related applications


Cr2+:ZnSe/CdSe/ZnS Single Frequency Tunable laser 2-3.5 µm

Diode pumped Tm fiber laser

Amplifier

Ho:YLF AOM

ZGP CdSe

OPG-OPA

Cr2+:II-VI SLM injection seeder Diode pumped Tm fiber laser

Absorption cell

Reference absorpber

Set of etalons

Power meter

FMSdetector

Gas inlet Detection & Calibration

• By rapidly tuning the wavelength of the OPG, the absorption of a gas mixture is measured as a function of the wavelength.

• The instrument will be capable of identifying a large variety of molecular organic trace-gases in multi-compound gas-mixtures and to quantify them at ultra-low concentration levels.

• The proposed instrument will provide a complete, total profile of the trace gas contents in complex gas mixtures in real-time, i.e. with response times in the order of seconds.

Exhaled Gas Sample

Diode pumped Er fiber laser

Diode pumped Er-fiber laser

Er:YAG

III. Develop laser system for detecting environmental contaminants and Counter-Terrorism related applications. Middle-IR Optical nose


COSS Researchers are currently developing Optical Power Limiting (OPL) technology for protection against wavelength tunable laser threats

• Another research area of the Center for Optical Sensors and Spectroscopies is the PROTECTION of optical sensors and eyes

• In December of 2004, The FBI and Department of Homeland Security sent out a memo warning that there is evidence that terrorists have explored using lasers as weapons to bring down commercial airliners


Chemical Structure of[(R-APPC)M]Cln Complexes

n+

N M

NN

NN

R

nCl

L

L

Theoretical and Experimental Studies of Excited State Absorbers

for Optical Power Limiting

PI: Chris Lawson, University of Alabama atBirmingham, [email protected]

RESEARCH GOAL: Develop new metal-organic complexes for power limiting applications, and study the relationship between chemical structure and optical nonlinearity in these complexes.

Expanded porphyrin complexes[(R-APPC)M]Cln (most promising yet)• Extensively delocalized π-conjugated

electron system (18-26 π electrons)• Broad region of low linear absorption

(480-660 nm)• High third order optical nonlinearities• Remarkable chemical and thermal

stability• Exhibit strong optical limiting via

reverse saturable absorption for nspulses, 532 nm.

• Easily-modified chemical structure- Can vary R group- Large variety of candidate metals, M- Many candidate axial ligands, L

(NC)2C2-CdTXP

Incident Fluence (J/cm2)

0.001 0.01 0.1 1 10

Tran

smitt

ance

0.0

0.1

0.2

0.3

0.4

0.5

0.6

experimental (5 ns)experimental (40 ps)theoretical (5 ns)theoretical (40 ps)

M. McKerns, W. Sun, C. Lawson, andG. Gray, “Higher-order triplet-triplet interaction in energy-level modeling of excited-state absorption for an expanded porphyrin cadmium complex”, accepted for publication, J. Opt. Soc. Am. B, 2004.

and

C. Byeon, et al., Appl. Phys. Lett. 84,5174 - 5176 (2004).

T1

T2

Tn

Sn

S2

S1

S0

10k

21k

42k

65k

53k

01σ

12σ

24σ56σ

35σ

30k

13k

25k

RECENT WORK:• Using 7-level theoretical model of nonlinear absorption to fit both ns and ps optical limiting data allows us to extract excited-state lifetimes and absorption cross-sections in expanded porphyrin complexes, and track population over duration of the excitation pulse. Increased knowledge of these complexes leads to appropriate changes in chemical structure and better optical limiting.• Currently carrying out synthesis of new expanded porphyrin materials with Cd, Ag and other metal centers and various axial ligands.


Journal Articles and Published Proceedings (2005-2006)1. A. Gallian, V. V. Fedorov, J. Kernal, J. Allman, S. B. Mirov, E. M. Dianov, A. O. Zabezhaylov, I. P. Kazakov, “Spectroscopic studies of

molecular-beam epitaxially grown Cr2+ -doped ZnSe thin films” Applied Physics Letters, v.86, 091105, (2005)2. A. Gallian, V. V. Fedorov, J. Kernal, S. B. Mirov, V. V. Badikov “Laser Oscillation at 2.4 µm from Cr2+ in ZnSe Optically Pumped over Cr

Ionization Transitions” in Advanced Solid-State Photonics 2005 Technical Digest on CD-ROM (The Optical Society of America, Washington, DC, 2005), MB12

3. A. Gallian , V. V. Fedorov, J. Kernal, J. Allman, S. Mirov, E. M. Dianov, A. O. Zabezhaylov, I. P. Kazakov,” En Route to Electrically Pumpable Cr2+ Doped II-VI Semiconductor Lasers” in Advanced Solid-State Photonics 2005 Technical Digest on CD-ROM (The Optical Society of America, Washington, DC, 2005), TuB14

4. I. S. Moskalev, V. V. Fedorov, S. B. Mirov, “Multiwavelength Mid-IR Spatially-Dispersive CW Laser Based on Polycrystalline Cr2+: ZnSe”, in Advanced Solid-State Photonics 2005 Technical Digest on CD-ROM (The Optical Society of America, Washington, DC, 2005), TuB12

5. A.G. Van Engen Spivey, V. V. Fedorov, S. B. Mirov, and Ch. M. Lawson “Amplification of narrow line LiF:F2+** color center laser oscillation”, Optics Communications, Volume 254 , Issues4-6 , Pages290-298 (2005)

6. J. Kernal, V. V. Fedorov, A. Gallian, S. B. Mirov, V. V. Badikov,”3.9-4.8 µm gain-switched lasing of Fe:ZnSe at room temperature”, Optics Express, Vol. 13, No. 26, pp. 10608 – 10615, (2005)

7. T.T. Basiev, M.N. Basieva, M.E. Doroshenko, V.V. Fedorov, V.V. Osiko, S.B. Mirov, “Stimulated Raman scattering in mid IR spectral range 2.31-2.75-3.7 µm in BaWO4 crystal under 1.9 and 1.56 µm pumping” Laser Physics Letters, Volume 3, pp17-20, (2006)

8. V. V. Fedorov, J. Kernal, A. Gallian, V. V. Badikov, S. B. Mirov, ”3.9-4.8 µm gain-switched lasing of Fe:ZnSe at room temperature,” in Solid State Lasers XV: Technology And Devices, Proceedings of SPIE 6100, San Jose, California USA, 21–26 January, (2006).

9. V.V. Fedorov, I. Moskalev, L. Luke, A. Gallian, S.B. Mirov ”Mid-infrared Electroluminescence of Cr2+ Ions in ZnSe Crystals” , in Advanced Solid-State Photonics 2006, WB21, Technical Digest on CD-ROM (The Optical Society of America, Washington, DC, 2006)

10. J. Kernal, V. Fedorov, A. Gallian, S. Mirov, V. Badikov, "Room Temperature 3.9-4.5 µm Gain-Switched Lasing of Fe:ZnSe", in Advanced Solid-State Photonics 2006, MD6, Technical Digest on CD-ROM (The Optical Society of America, Washington, DC, 2006)

11. I. S. Moskalev, V.V. Fedorov , S.B. Mirov,A.Babushkin, V.P.Gapontsev, D.V.Gapontsev, N.Platonov, "Efficient Ho:YAG Laser Resonantly Pumped by Tm-Fiber Laser", in Advanced Solid-State Photonics 2006, TuB10, Technical Digest on CD-ROM (The Optical Society of America, Washington, DC, 2006)

12. T. Basiev, M. N. Basieva, M. E. Doroshenko, V. V. Fedorov, V. V. Osiko1, S. B. Mirov,"Stimulated Raman Scattering in the Mid IR Range 2.31-2.75-3.7 µm in a BaWO4 Crystal under 1.9 and 1.56 µm Pumping", in Advanced Solid-State Photonics 2006, MB10, Technical Digest on CD-ROM (The Optical Society of America, Washington, DC, 2006)

13. Marquecho, R. and R. Pitt (2005). “Metal Associations with Stormwater Particulates,” 78th Annual Water Environment Federation Technical Exposition and Conference. Washington, D.C. Oct. 29 – Nov. 2, 2005.

14. Pitt, R., A. Maestre, and R. Morquecho. “A National Stormwater Quality Database, part 1,” invited feature article. Watershed/Wet Weather Technical Bulletin, Water Environment Federation. 2005.

15. Pitt, R. and A. Maestre. “A National Stormwater Quality Database, part 2,” invited feature article. Watershed/Wet Weather Technical Bulletin, Water Environment Federation. 2005.

16. Clark, S., M.M. Lalor, and R. Pitt. “Wet-weather pollution from commonly-used building materials.” World Water and Environmental Resources Congress. ASCE/EWRI. Anchorage, Alaska. May 2005. (conference CD-ROM).

17. Pratap, M., U. Khambhammettu, S. Clark, and R. Pitt. “Stormwater treatment using upflow filters.” World Water and Environmental Resources Congress. ASCE/EWRI. Anchorage, Alaska. May 2005. (conference CD-ROM).

18. Morquecho, R. and R. Pitt. “Pollutant associations with particulates in stormwater.” World Water and Environmental Resources Congress. ASCE/EWRI. Anchorage, Alaska. May 2005. (conference CD-ROM).


Chapters in Books (2005-2006)

1. I.S.Moskalev, V.V.Fedorov, T.T.Basiev, P.G.Zverev, S.B.Mirov, "Application of laser beam shaping for spectral control of "spatially dispersive" lasers" in Laser Beam Shaping Applications, Dickey, Holswade, Shealy - Eds., Marcel & Dekker ISBN: 0824759419, (2005).

2. Maestre, A. and R. Pitt. “Observations from the National Stormwater Quality Database.” In: Stormwater and Urban Water Systems Modeling, Monograph 14. (edited by W. James, K.N. Irvine, E.A. McBean, and R.E. Pitt). CHI. Guelph, Ontario, to be published in 2006.

3. Clark, S.E., R. Pitt, P.D. Johnson, S. Gill, and M. Pratap. “Media filtration to remove solids and associated pollutants from stormwater runoff.” Best Management Practices (BMP) Technology Symposium: Current and Future Directions, American Society of Civil Engineers. 2005.

4. Maestre, A., R. Pitt, S.R. Durrans, and S. Chakraborti. “Stormwater quality descriptions using the three parameter lognormal distribution.” Effective Modeling of Urban Water Systems, Monograph 13. (edited by W. James, K.N. Irvine, E.A. McBean, and R.E. Pitt). CHI. Guelph, Ontario, pp. 247 – 274. 2005.

5. Pitt, R., R. Bannerman, S. Clark, and D. Williamson. “Sources of pollutants in urban areas (Part 1) – Older monitoring projects.” In: Effective Modeling of Urban Water Systems, Monograph 13. (edited by W. James, K.N. Irvine, E.A. McBean, and R.E. Pitt). CHI. Guelph, Ontario, pp. 465 – 484 and 507 – 530. 2005.

6. Pitt, R., R. Bannerman, S. Clark, and D. Williamson. “Sources of pollutants in urban areas (Part 2) – Recent sheetflow monitoring results.” In: Effective Modeling of Urban Water Systems, Monograph 13. (edited by W. James, K.N. Irvine, E.A. McBean, and R.E. Pitt). CHI. Guelph, Ontario, pp. 485 – 530. 2005.


Conference presentations (2005-2006)1. A. Gallian, V.V. Fedorov, Sergey B. Mirov, V. V. Badikov, S. N. Galkin, E. F. Voronkin, A. I. Lalayants “Hot-Pressed Ceramic

Cr2+:ZnSe Gain-Switched Laser,” in Conference on Lasers and Electro-Optics/Quantum Electronics and Laser Science and Photonic Applications, Systems and Technologies 2005 (Optical Society of America, Washington, DC, 2005), CME6.

2. A. Gallian, V.V. Fedorov, I. S. Moskalev, Sergey B. Mirov, V. V. Badikov, “Cr2+:ZnSe Laser Pumped over Cr Ionization Transitions,” in Conference on Lasers and Electro-Optics/Quantum Electronics and Laser Science and Photonic Applications, Systems and Technologies 2005 (Optical Society of America, Washington, DC, 2005), CTuA4.

3. A.Gallian, V.V.Fedorov, I.S. Moskalev, S.B.Mirov, V.V. Badikov “Cr2+:ZnSe Laser Pumped Utilizing Cr Ionization”, International Conference on Coherent and Nonlinear Optics and International Conference on Lasers, Applications, and Technologies (ICONO/LAT) , St. Petersburg, Russia, May 11-15, (2005).

4. S. B. Mirov, V. V. Fedorov, J. Kernal, A. Gallian, V. V. Badikov, “3.9-4.5 µm gain-switched lasing of Fe:ZnSe at room temperature”Mid-Infrared Coherent Sources Conference , Barcelona (Spain) 6-11 November (2005).

5. J. Allman, A.O. Zabezhaylov, E.M. Dianov, I.P. Kazakov, S.B. Mirov, V.V. Fedorov, A. Gallian, J.Kernal, ” MBE Growth and study of Cr2+:ZnSe Layers for Mid-IR Lasers”, 13th Int. Symp. “Nanostructures: Physics and Technology” , St Petersburg, Russia, June 20–25, (2005).

6. I.S. Moskalev, V.V. Fedorov, S.B. Mirov , “Multiwavelength, ultrabroadband semiconductor and solid-state spatially-dispersive lasers” , in Technical Digest of Optics in the Southeast , p. 154, Atlanta, USA (2005).

7. R. A. Sims, J. Kernal, V. V. Fedorov, S. B. Mirov, “Co:ZnS and Co:ZnSe saturable absorbers for alexandrite laser”, in Technical Digest of Optics in the Southeast , p. 65, Atlanta, USA (2005).

8. A.Gallian, V.V.Fedorov, L. Luke, I.S. Moskalev, S.B.Mirov, V.V. Badikov, “Cr2+:ZnSe Laser Pumped Utilizing Cr Ionization”, Technical Digest of Optics in the Southeast , p. 66, Atlanta, USA (2005).

9. R. A. Sims, J. Kernal, V. V. Fedorov, S. B. Mirov, “Characterization of cobalt doped ZnSe and ZnS crystals as saturable absorbers for alexandrite lasers”, Solid State Lasers XV: Technology And Devices , [6100-22] San Jose, California USA, 21–26 January (2006).

10. L. Luke, V. V. Fedorov, I. S. Moskalev, A. Gallian, S. B. Mirov, “Middle-infrared electroluminescence of n-type Cr doped ZnSe crystals”, Solid State Lasers XV: Technology And Devices , [6100-26] San Jose, California USA, 21–26 January , (2006).

11. Marquecho, R. and R. Pitt (2005). “Metal Associations with Stormwater Particulates,” 78th Annual Water Environment Federation Technical Exposition and Conference. Washington, D.C. Oct. 29 – Nov. 2, 2005.

12. Pitt, R. and A. Maestre. “Stormwater quality as described in the National Stormwater Quality Database.” 10th International Conference on Urban Drainage, Copenhagen, Denmark. August 21-26, 2005.

13. Clark, S.E., M.M. Lalor, R. Pitt, and R. Field. “Wet-weather pollution from commonly-used building materials.” 10th International Conference on Urban Drainage, Copenhagen, Denmark. August 21-26, 2005.

14. Clark, S.E., P. Johnson, R. Pitt, S. Gill, and M. Pratap. “Filtration for metals removal from stormwater.”10th International Conference on Urban Drainage, Copenhagen, Denmark. August 21-26, 2005.

15. Clark, S., M.M. Lalor, and R. Pitt. “Wet-weather pollution from commonly-used building materials.” World Water and Environmental Resources Congress. ASCE/EWRI. Anchorage, Alaska. May 2005.

16. Pratap, M., U. Khambhammettu, S. Clark, and R. Pitt. “Stormwater treatment using upflow filters.” World Water and Environmental Resources Congress. ASCE/EWRI. Anchorage, Alaska. May 2005.

17. Morquecho, R. and R. Pitt. “Chemical forms and effects of heavy metals in stormwater.” World Water and Environmental Resources Congress. ASCE/EWRI. Anchorage, Alaska. May 2005.


Patents (2005-2006)

• US patent # 6,960,486 November 1, 2005• 2 US patent applications filed

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