NIR-PHOTOMULTIPLIER TUBES AND THEIR APPLICATIONS NIR ...

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Rose Bengal in pure water. SAMPLE TEMPERATURE. SAMPLE TEMPERATURE. Detector: NIR-PMT R5509-43. ( ) room temperature. ( ) room temperature. ( ).
NIR-PHOTOMULTIPLIER TUBES AND THEIR APPLICATIONS NIR-PMTs (near-infrared photomultiplier tubes) are photodetectors that provide high-speed response and high sensitivity in the near infrared region. These are ideal for detecting high-speed phenomena occurring at low light levels such as in measurements of photoluminescence, fluorescence lifetime, Raman spectroscopy, cathode luminescence, and singlet-oxygen emissions. As major NIR-PMT products, Hamamatsu offers the R5509 series photomultiplier tubes (spectral response range: 300 nm to 1400 nm or 300 nm to 1700 nm) and the H10330A series NIR-PMT modules (spectral response range: 950 nm to 1200 nm, 950 nm to 1400 nm, or 950 nm to 1700 nm) that contain a thermoelectric cooler and high-voltage power supply. Either type can be used over a wide measurement range from analog detection mode to photon counting mode. This brochure introduces major applications that utilize the unique features of NIR-PMTs.

Q. What can we do with near infrared light? 1. Semiconductor quality control and material evaluation – Photoluminescence measurement 2. Evaluation of quantum devices and photonic crystals – Photoluminescence measurement 3. Evaluation of molecular structures – Raman spectroscopy 4. Reactive oxygen study – Singlet-oxygen emission measurement 5. Environment measurement – Light detection and ranging (LIDAR)

THERMOELECTRIC COOLED NIR-PMT MODULE H10330A SERIES

NIR-PMT R5509 SERIES

No Liquid Nitrogen, No Cooling Water is Necessary

Wide Spectral Response from Visible to Near Infrared

●Spectral Response

●Spectral Response

TPMOB0200EC

CATHODE RADIANT SENSITIVITY (mA/W) QUANTUM EFFICIENCY (%)

CATHODE RADIANT SENSITIVITY 101

R5509-73

-75

-45 QUANTUM EFFICIENCY

100

10-1

at -80 °C

TPMHB0426EF

102

H10330A-25

10-2

10-3 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800

WAVELENGTH (nm)

CATHODE RADIANT SENSITIVITY (mA/W) QUANTUM EFFICIENCY (%)

102

CATHODE RADIANT SENSITIVITY

101

100

QUANTUM EFFICIENCY R5509-43

10-1

10-2 200

400

600

800 1000 1200 1400 1600 1800

WAVELENGTH (nm) * C9940 series cooler is necessary for operation.

THERMOELECTRIC COOLED

NIR-PMT MODULE H10330A-25/-45/-75 OVER VIEW The H10330A series is the NIR-PMT module using a compact NIR-PMT (near-infrared photomultiplier tube) developed by our advanced photocathode technology. The NIR-PMT is contained in a thermally insulated sealed-off housing evacuated to a high vacuum. The internal thermoelectric cooler eliminates the need for liquid nitrogen and cooling water. The light input window of these modules use a condenser lens to provide a virtually larger photosensitive area allowing easy optical coupling. Adapters for connection to an optical fiber and monochromator are also available as options.

OUTPUT WAVEFORM

FEATURES

Rise Time: 0.9 ns, T.T.S.: 0.4 ns

●Simple Operation by Air Cooled TE Cooler

No Liquid Nitrogen, No Cooling Water is Necessary

●Operable in 20 min after Switched ON ●Large Detection Area 18 mm for Collimated Light

●HV Power Supply with Interlock Function ●Optional Adapters are Available

TPMOB0163EB

OUTPUT VOLTAGE (20 mV/Div.)

●Compact and lightweight due to vacuum sealedoff thermal insulation technology ●High Sensitivity (Applicable to Photon Counting) ●Fast Time Response

For Optical Fiber For Monochromator

SUPPLY VOLTAGE : -800 V : 0.85 ns RISE TIME : 1.65 ns FALL TIME PULSE WIDTH : 1.63 ns WAVELENGTH : 1300 nm LOAD RESISTOR : 50 Ω

TIME (2 ns/Div.)

SELECTION GUIDE / SPECIFICATIONS Type No. Photocathode Material Spectral Response Detection Area for Collimated Light Effective Area of PMT Cathode Sensitivity Quantum Efficiency Gain Anode Pulse Rise Time Anode Pulse Fall Time Time Response Transit Time Spread (T.T.S) Main Application

H10330A-25

H10330A-45 InP / InGaAsP 950 nm to 1200 nm 950 nm to 1400 nm 18 mm 1.6 mm 2 % Typ. 1 × 106 0.9 ns 1.7 ns 0.4 ns YAG laser (1.06 µm) measure- Singlet-oxygen emmision measurement, ment, Si Photoluminescence, Si Photoluminescence Laser rader (LIDAR)

H10330A-75 InP / InGaAs 950 nm to 1700nm

Optical communication device evaluation, Laser rader (LIDAR)

TEMPERATURE / DARK CURRENT vs. COOLING TIME (H10330A-45) ANODE DARK CURRENT (nA)

70

SYSTEM CONFIGURATION (CONNECTION DIAGRAM)

TPMOB0162EC

NIR-PMT MODULE

60 NIR-PMT MODULE

RESISTOR BOX WITH BNC CONNECTORS (100 kΩ)

DARK CURRENT 50

NIR-PMT MODULE CONTROLLER VOLTAGE

ERROR

40

[V] STANDBY

READY OUTPUT

HIGH VOLTAGE CABLE (2.5 m)

POWER

30 OUTPUT ADJ.

20 CONTROL CABLE (2.5 m)

NIR-PMT MODULE CONTROLLER

10 0

TPMOC0199EA

0

5

10

15

20

25

COOLING TIME (min)

DIMENSIONAL OUTLINE (Unit: mm) ●NIR-PMT Module

4

150 42.5

50

FAN EXHAUST VENT*

100

* Do not block the air intake vents and fan exhaust vent. Otherwise, heat builds up in the unit causing poor performance or failure.

80

31

88

12 23

AIR INTAKE VENTS* 13.9

25.7

NIR-PMT MODULE

50

M30 P=0.5

BNCRECEPTACLE

CONDENSER LENS

48

SHVRECEPTACLE

60

CONTROLLER INPUT

INPUT WINDOW EFFECTIVE 15.5 AREA 18

12

100

23.5

PHOTOCATHODE

70

59.5

163

SIGNAL

120

25.5

10 PIN CONNECTOR

49

4-M4**

70

** The rubber feet are mounted with M4 screws. If they are removed, the screw holes (M4) can be used for fixing purpose.

TPMOA0040EB

●NIR-PMT Module Controller 102

26

279.5

20

26

55 31

VOLTAGE

AC INPUT OUTPUT

ERROR

[V] STANDBY

READY

55

AC INPUT CONTROLLER

40

OUTPUT ADJ.

100

130

OUTPUT

POWER

12

12

NIR-PMT MODULE CONTROLLER

70

15.5

248

10 PIN CONNECTOR

SHVRECEPTACLE

TPMOA0041EB

NIR-PMTs (near-infrared photomultiplier tubes) (near-infrared: 1.4 µm / 1.7 µm)

R5509-43/-73 OVER VIEW Hamamatsu near infrared photomultiplier tubes (NIRPMT) R5509-43 and -73 have photocathodes with extended spectral response ranges to 1.4 µm or 1.7 µm where beyond 1.1 µm have been the limit of conventional photocathodes. The R5509-43 is recommended for detection up to 1.35 µm, while the R5509-73 is up to 1.7 µm. For operation, exclusive cooler C9940 series is necessary.

OUTPUT WAVEFORM (R5509-43)

FEATURES ●High sensitivity enables accurate PL (Photoluminescence) measurement with a low excitation power that could not be obtained with a strong excitation. ●Flat response from visible to near IR minimizes spectral sensitivity correction. The spectral response covers a wide range from 0.3 µm to 1.4 µm or 1.7 µm.

●Photoluminescence from a room temperature sample can be measured.* High sensitivity enables weak light emission measurement.

●Time resolved measurement in near IR is realized.

OUTPUT VOLTAGE [1 mV/Div]

High gain and low noise improve the detection limit.

TPMHB0406EB

SUPPLY VOLTAGE : -1500 V : 2.60 ns RISE TIME : 6.36 ns FALL TIME : 3.58 ns PULSE WIDTH : 1300 nm WAVELENGTH AMBIENT TEMPERATURE

: -80 °C

Fast time response (Rise time): 3 ns. * Detection limit depends on the material and measurement condition.

TIME [5 ns/Div]

SPECIFICATIONS Type Spectral Response Photocathode Material Minimum Effective Area Recommended Operating Temperature Cathode Sensitivity Quantum Efficiency Gain Anode Pulse Rise Time Time Response Anode Pulse Fall Time Transit Time Spread (T.T.S)

R5509-43 300 nm to 1400 nm InP / InGaAsP

R5509-73 300 nm to 1700 nm InP / InGaAs

3 mm × 8 mm -80 °C 2 % Typ. (at 1300 nm: R5509-43, at 1500 nm: R5509-73) 1 × 106 3 ns 23 ns 1.5 ns

DIMENSIONAL OUTLINE (Unit: mm) 51 ± 1

Top View 33° ± 2

3

°

PIN No.3

APERTURE

8

PIN No.1

90

PHOTOCATHODE (3 × 8)

°± 5° 2.

15°

20

PIN No.14

Bottom View

88 ± 2

HA COATING

IC IC IC IC P 7

PHOTOCATHODE

8

9

DY10 6 DY8 5 DY6

LIGHT SHIELD

4 3

2 DY4 1 DY2 K

14 MAX.

DY9 DY7

10 11 12

13 DY5 14 15 DY3 16 DY1 17 IC DY : Dynode 18 B K : Photocathode 19 P : Anode IC 20 21 IC

IC

B : Bias Electrode IC : Internal Connection (Do not use)

SHORT PIN TPMHA0283EC

TPMHA0284ED

RELATED PRODUCTS Exclusive coolers C9940-01/-02 The C9940-01/-02 are exclusive coolers for R5509 series photomultiplier tubes. To operate the R5509 series, it is necessary to cool it down to -70 °C to -90 °C range (recommended temperature: -80 °C). Cooling suppresses dark current and improves signal to noise ratio to make weak near infrared light measurements possible with high sensitivity. Two types are available with different line voltage regulations, 100 V to 115 V (C994001) and 230 V (C9940-02) .

■FEATURES

●Temperature range: -70 °C to -90 °C ●Voltage divider, Magnetic shield case included ●Alarm with output when liquid nitrogen is running out ●No external dry nitrogen is required

■SYSTEM CONFIGURATION PMT COOLER HOUSING PMT

PMT SOCKET ASSEMBLY CONTROLL CABLE

100 kΩ LOAD REGISTER BOX

HEAT INSULATING HOSE COOLER LIQUID NITROGEN SUCTION PIPE

VINYL TUBE

■OTHER ACCESSORIES REQUIRED

AC POWER CABLE

COOLER CONTROLLER

POWER SWITCH TEMPERATURE CONTROLLER

LIQUID NITROGEN CONTAINER (NOT INCLUDED) TACCC0123EB

●Liquid nitrogen container From 10 L to 25 L capacity The opening of the container should allow the 15 mm diameter liquid nitrogen suction pipe to be inserted. ●High voltage power supply Capable to provide stable output of -1500 V, 0.2 mA Recommended : C4840 ●High voltage cable with an SHV-P connector Recommended : E1168-17 ●Signal COAX cable with a BNC-P connector Recommended : E1168-05

APPLICATION EXAMPLES Photoluminescence measurement Sample

InAlAs/InGaAs

SAMPLE TEMPERATURE

77K

Sample structure: InAlAs/InGaAs (SQWs)/InP(sub)

single quantum wells

InGaAs InAlAs InGaAs InAlAs InGaAs InAlAs InGaAs InAlAs Fe doped 50 Å 300 Å 30 Å 300 Å 60 Å 300 Å 100 Å 3000 Å InP (100) sub.

EXCITATION LIGHT: SHG Nd: YAG (532 nm) SLIT: 0.2 mm × 0.2 mm 100 Å SAMPLE TEMPERATURE: 77K

60 Å

30 Å

INTENSITY (RELATIVE)

Photoluminescence spectra emitted from a sample with different InGaAs well widths. This data proves that intensity distribution of the spectrum corresponding to each quantum well varies with the excitation light power.

EXCITATION LIGHT POWER: 8 µW EXCITATION LIGHT POWER: 0.05 mW EXCITATION LIGHT POWER: 0.6 mW EXCITATION LIGHT POWER: 3 mW 1100

1200

1300

1400

1500

1600

1700

WAVELENGTH (nm) TPMHB0627EB

Detector: NIR-PMT R5509-73

Undoped SI-InP

SAMPLE TEMPERATURE

300K (room temperature)

EXCITATION LIGHT: SHG Nd: YAG (532 nm) SLIT: 0.5 mm × 0.5 mm SAMPLE TEMPERATURE: 300K

INTENSITY (RELATIVE)

Sample

Emission from deep levels in a semi-insulating InP substrate at room temperature was clearly observed.

X10 EXCITATION LIGHT POWER: 0.6 mW X1

EXCITATION LIGHT POWER: 3 mW X10

X1 800

900

1000

1100

1200

1300

1400

1500

1600

WAVELENGTH (nm) TPMHB0621EB

SAMPLE TEMPERATURE

77K

EXCITATION LIGHT : SHG Nd: YAG (532 nm) SLIT: 0.5 mm × 0.5 mm SAMPLE TEMPERATURE: 77K

INTENSITY (RELATIVE)

Data shows that intensity distribution of the photoluminescence spectrum changes with excitation light power. Using a "low power excitation light" allows highprecision measurement not subject to variations in excitation light intensity. It is therefore essential to use "low power excitation light" in order to measure emission from deep levels and total band-to-band transition.

EXCITATION LIGHT POWER: 0.05 mW

EXCITATION LIGHT POWER: 0.6 mW

EXCITATION LIGHT POWER: 3 mW 800

900

1000

1100

1200

1300

1400

1500

1600

WAVELENGTH (nm) TPMHB0622EA

Detector: NIR-PMT R5509-73

APPLICATION NOTE Photoluminescence measurement Undoped SI-GaAs

SAMPLE TEMPERATURE

300K (room temperature)

Emission from deep levels in a semi-insulating GaAs substrate at room temperatures was clearly observed.

EXCITATION LIGHT: SHG Nd: YAG (532 nm) SLIT: 0.5 mm × 0.5 mm SAMPLE TEMPERATURE: 300K

INTENSITY (RELATIVE)

Sample

EXCITATION LIGHT POWER: 0.6 mW

EXCITATION LIGHT POWER: 3 mW 700

800

900

1000 1100 1200 1300 1400 1500 1600 1700

WAVELENGTH (nm)

TPMHB0619EA

SAMPLE TEMPERATURE

77K INTENSITY (RELATIVE)

EXCITATION LIGHT: SHG Nd: YAG (532 nm) SLIT: 0.5 mm × 0.5 mm SAMPLE TEMPERATURE: 77K

EXCITATION LIGHT POWER: 2 nW

700

800

900

1000 1100 1200 1300 1400 1500 1600 1700

WAVELENGTH (nm)

TPMHB0620EA

Detector: NIR-PMT R5509-73

InAs/InGaAs quantum dots structure Figure shows PL spectrum at the room temperature from InAs quantum dots covered with InGaAs layer. Size and uniformity of quantum dots can be estimated from the peak wavelength and the FWHM of PL spectrum. However, when excitation power is increased, luminescence of shorter wavelength (1200 nm) becomes strong, and the estimate of exact peak wavelength and the FWHM becomes impossible. Therefore, it is important that excitation power must be kept as weak as possible for precise measurement. For this reason, a high sensitivity detector is required.

SAMPLE TEMPERATURE

300K (room temperature)

EXCITATION LIGHT: SHG Nd: YAG (532 nm) SLIT: 0.2 mm / 0.2 mm SAMPLE TEMPERATURE: 300 K

INTENSITY (RELATIVE)

Sample

EXCITATION LIGHT 30 mW 3 mW 0.3 mW 0.03 mW 3 µW 1050

1100

1150

1250

Basic Structure InGaAs

15 nm

InGaAs

5 nm

InAs dots

GaAs buffer

300 nm

GaAs (100) substrate

Detector: NIR-PMT R5509-43

1200

1300

WAVELENGTH (nm)

1350

1400

1450 TPMHB0664EA

APPLICATION EXAMPLES Photoluminescence measurement Sample

SAMPLE TEMPERATURE

low resistivity wafer ρ > 0.02 kΩcm

300K (room temperature)

Silicon, the indirect bandgap semiconductor, has lower photoluminescence emission compared with direct bandgap semiconductors such as GaAs, InP, etc. However, the NIR-PMT has made it possible to observe a clear photoluminescence spectra from a room temperature silicon wafer even at low power excitation lights.

EXCITATION LIGHT: SHG Nd: YAG (532 nm) SLIT: 0.5 mm × 0.5 mm SAMPLE TEMPERATURE: 300K

INTENSITY (RELATIVE)

B-Dope Si (111)

EXCITATION LIGHT POWER: 0.05 mW

EXCITATION LIGHT POWER: 0.6 mW EXCITATION LIGHT POWER: 3 mW 900

1000

1100

1200

1300

1400

WAVELENGTH (nm)

TPMHB0623EA

SAMPLE TEMPERATURE

77K INTENSITY (RELATIVE)

EXCITATION LIGHT: SHG Nd: YAG (532 nm) SLIT: 0.05 mm × 0.05 mm SAMPLE TEMPERATURE: 77K

EXCITATION LIGHT POWER: 3 mW

900

1000

Detector: NIR-PMT R5509-43

Sample

1200

1300

1400 TPMHB0624EA

SAMPLE TEMPERATURE

Basic Structure p - InGaAsP 2 µm

p + InP 2 µm

EXCITATION LIGHT: SHG Nd: YAG (532 nm) SLIT: 0.5 mm × 0.5 mm SAMPLE TEMPERATURE: 300K

INTENSITY (RELATIVE)

300K (room temperature)

InGaAsP/InP p - InP 0.02 µm 2 × 1016 cm-3

1100

WAVELENGTH (nm)

EXCITATION LIGHT POWER: 0.6 mW

p + InP SUB 350 µm

EXCITATION LIGHT POWER: 3 mW TPMHC0187EB

1100

An epitaxial wafer at the room temperature can be evaluated.

1200

1300

1400

1500

1600

1700

WAVELENGTH (nm)

TPMHB0617EA

SAMPLE TEMPERATURE

77K

EXCITATION LIGHT: SHG Nd: YAG (532 nm) SLIT: 0.2 mm × 0.2 mm SAMPLE TEMPERATURE: 77K

INTENSITY (RELATIVE)

Photoluminescence measurement in 77 K sample is possible at low power excitation lights from a few to tens of micro-watts.

EXCITATION LIGHT POWER: 8 µW

EXCITATION LIGHT POWER: 0.05 mW

EXCITATION LIGHT POWER: 0.6 mW

EXCITATION LIGHT POWER: 3 mW 1100

1200

1300

1400

1500

WAVELENGTH (nm)

Detector: NIR-PMT R5509-43

1600

1700 TPMHB0618EA

APPLICATION NOTE Photoluminescence measurement Sample

β-FeSi2

6

5

INTENSITY (mV)

The NIR-PMT measures the photoluminescence of β-FeSi2 currently being studied for use as an environmentally-friendly semiconductor material. This β-FeSi2 sample is a silicide thin film grown by Fe-irradiation onto a silicon (111) substrate kept at a high temperature. As can be seen from the graph on the right, the photoluminescence intensity at a sample temperature of 77 K is at least 30 times higher than at 300 K. The peak wavelength of the 77 K sample occurs at 1562 nm while that of the 300 K sample shifts slightly to 1585 nm. (The longer wavelength side is limited by the photomultiplier tube sensitivity.)

EXCITATION LIGHT: SHG Nd: YAG (532 nm) 0.2 mJ, 10 ns, 20 Hz

4

SAMPLE TEMPERATURE: 77 K

3

2 ×10 1

0 1300

SAMPLE TEMPERATURE: 300 K (ROOM TEMPERATURE) 1400

1500

1600

1700

WAVELENGTH (nm) TPMHB0783EA

Detector: NIR-PMT R5509-73

Cathodeluminescence (CL) measurement Sample

SAMPLE TEMPERATURE

10K

InAs/InP

Cathodoluminescence (CL) Measurement When a sample is irradiated by high-velocity electron beams, electron-hole pairs in the sample are excited and then recombine while producing a characteristic luminescence known as cathodoluminescence (CL). Information on the internal electron structures of the sample can be studied by measuring this luminescence.

Condition Accelerating Voltage Current

Detector: NIR-PMT R5509-43

Ge PIN-PD 77 K

The data on the right show images of cathodoluminescence (CL) emitted from InAs islands in an InAs/InP multiple quantum well structure, observed with a scanning electron microscope (SEM) to which a light collection system and a monochromator were installed. The right-hand CL images were taken with the SEM using a Ge PIN photodiode. These images are not clear due to external noise such as cosmic rays. In contrast, the lefthand data taken with an R5509-43 photomultiplier tube shows clear, sharp CL images with a high S/N ratio. The R5509-43 allows high-sensitivity CL measurements in the near infrared region, which are expected to prove useful in optical evaluations of samples, analysis of inorganic or organic substances, and other near infrared spectroscopy.

Electron Probe

R5509-43

5 kV 10 nA

990 nm

990 nm

1010 nm

1020 nm

1030 nm

1040 nm

Photos: By courtesy of Prof. Y. Takeda, Dept. of Materials Science and Engineering, Graduate School of Engineering, Nagoya University; Prof. A. Nakamura, Center for Integrated Research in Science and Engineering, Nagoya University

APPLICATION EXAMPLES Fluorescence lifetime measurement Sample

InAs Quantum Dots

SAMPLE TEMPERATURE

300K (room temperature)

104 EXCITATION: YAG (1064 nm), WIDTH: 1.15 ns WAVELENGTH: 1274 nm

Data shown here is photoluminescence lifetime from InAs quantum dots grown on an InGaAs substrate, measured with time-correlated single photon counting (TCSPC) technique.

103

INTENSITY

Decay & Fitting τ1 = 225 ps, τ2 = 1.4 ns

102

Basic Structure

Instrument Response

101

InAs QDs InGaAs 15 nm

100

0

2.5

5.0

7.5

10.0

InGaAs 5 nm

TIME (ns) TPMHB0784EA

GaAs buffer 300 nm

GaAs (100) substrate

Detector: Detector equivalent to the H10330A-45 NIR-PMT module System: Near-infrared lifetime measurement system C7990 series

Fluorescence lifetime measurement InGaAsP NIR-PMTs allow making fluorescence lifetime measurements in the near infrared region. Up till now this has been difficult to measure with conventional detectors. This measurement shows the fluorescence lifetime of a compound semiconductor (at room temperature).

SAMPLE TEMPERATURE

300K (room temperature)

IR3 (Decay+IRF4k) InP (0.4 µm), GaInAs InP (0.4 µm), GaInAs InP (0.4 µm), GaInAs Fit Results τ1 430.79 ns χ2 1.266

103

COUNT

Sample

102

0

100

200

300

400

500

600

700

800

900

RESIDUALS

TIME (ns) 5.7 0.0 -5.7

TPMHB0785EA

EXCITATION: Nd: YAG (1064 nm) FLUORECENT WAVELENGTH: 1347 nm SAMPLE TEMPERATURE: 300 K τ=430.79 ns was obtained after deconvolusion by the software.

Detector: Detector equivalent to the H10330A-75 NIR-PMT module System: Near-infrared life time measurement system C7990 series

APPLICATION NOTE Measurement of Raman spectroscopy Sample

Rhodamine B in Ethanol Solution (20 µmol/L)

SAMPLE TEMPERATURE

300K (room temperature)

EXCITATION LIGHT: LD-PUMPED ND: YAG (1064 nm) 10 mW, 10 ns pulse, 10 kHz SAMPLE TEMPERATURE: 77 K RHODAMINE B POWDER

INTENSITY

Raman spectroscopy is effective in studying the structure of molecules in a solution. In particular, near infrared Raman spectroscopy enables measurement of samples which were previously impossible with conventional methods using visible light excitation because of the influence of fluorescence. In this application, clear Raman spectra of solute rhodamine B (marked by ▼) are measured, as well as a Raman spectrum of ethanol solution. This data was obtained with weak excitation light averaging 10 mW output using pulsed excitation light and gate detection method under fluorescent room lighting conditions.

SAMPLE ETHANOL

1600

1400

1200

RAMAN SHIFT

1000

800

(cm-1) TPMHB0452EB

Detector: Detector equivalent to the H10330A-45 NIR-PMT module

Measurement of singlet oxygen Singlet oxygen Rose Bengal in pure water

SAMPLE TEMPERATURE

300K (room temperature)

2

Using the R5509-43 and a pulsed laser, singlet oxygen emission with a peak at 1270 nm were efficiently detected by signal processing with a gated pulse counter, reducing effects of fluorescence.

GATED PHOTON COUNTING METHOD EXCITATION LIGHT: PULSE SHG Nd: YAG (532 nm) 12 mJ, PULSE WIDTH: 10 ns, 20 Hz SLIT: 2 mm / 2 mm GATED DELAY TIME: 1.5 µs GATE TIME: 5 µs

1.8

INTENSITY (RELATIVE)

Sample

(Data obtained by CW YAG laser excitation is also shown in the same graph for comparison.)

1.6 1.4 1.2

CW 1 0.8 0.6 0.4 0.2

GATED PHOTON COUNTING METHOD

0 1150

1200

1250

1300

1350

1400

WAVELENGTH (nm)

SAMPLE TEMPERATURE

300K (room temperature)

105

SIGNAL OUTPUT (COUNTS)

The graph on the right shows detection limits evaluated by changing the concentration of the photosensitizer Rose Bengal. This proves that emissions from singlet oxygen of low concentration, even only 1 nmol/L, can be detected.

104

EXCITATION LIGHT: PULSE SHG Nd: YAG (532 nm) 12 mJ, PULSE WIDTH: 10 ns, 20 Hz SLIT: 2 mm / 2 mm CONCENTRATION OF ROSE BENGAL 10 µmol/L 1 µmol/L 1 nmol/L

103

102

101 1150

Detector: NIR-PMT R5509-43

TPMHB0665EB

1200

1250

1300

WAVELENGTH (nm)

1350

1400 TPMHB0666EB

APPLICATION EXAMPLES Measurement of singlet oxygen Rose Bengal in acetone, methanol and water

104

300K room (temperature)

Lifetime characteristics and emission spectrum of the singlet oxygen when the photosensitizer Rose Bengal was dissolved in acetone, methanol and water were measured.

103 τ=62 µs in CH3COCH3 (ACETONE) 102 τ=11 µs in CH3OH (METHANOL) 101 τ=3.7 µs in H2O (WATER) 100

0

10

20

30

1.4 × 104

300K (room temperature)

80

90

100 TPMHB0667EA

0.6 × 104

CH3OH

CH3COCH3

H2O

0.4 × 104 0.2 × 104

1220

1240

1260

1280

1300

1320

1340

WAVELENGTH (nm)

■Temporal change of 1O2 production

TPMHB0668EA

EXCITATION: 240 mW/cm2

EXCITATION: 160 mW/cm2

300

300

300

250

250

250

PHOTON COUNTS

PHOTON COUNTS

EXCITATION: 80 mW/cm2

200 150

with 5-ALA

100 50 0 0

100

200

300

TIME (s)

200 with 5-ALA

150 100 50

without 5-ALA

400

0 0

without 5-ALA

100

200

with 5-ALA

150 100

without 5-ALA

50

200

300

400

0 0

100

300

200

400

TIME (s)

TIME (s)

■Cumulative 1O2 counts during PDT at each fluence rate ■Proportion of cell death after PDT at each fluence rate 100

1800 1600 1400

CELL VIABILITY (%)

CUMULATIVE 1O2 COUNTS

Experimental conditions Photosensitizer: 5-ALA Cancer cells: Rat brain tumor cells 9L Excitation light: 635 nm

70

0.8 × 104

1.0 × 104

0 1200

In photodynamic therapy (PDT), singlet oxygen plays an important role in killing tumor cells. Changes in the amount of generated singlet oxygen can be observed at the cellular level. This implies that monitoring the singlet oxygen is the key to setting optimal PDT laser irradiation conditions. Accurate measurements can be made since NIR-PMT modules can directly capture weak singlet-oxygen emissions (1270 nm) from cells.

60

EXCITATION LIGHT: PULSE SHG Nd: YAG (532 nm) 2.5 mJ, PULSE WIDTH: 10 ns, 20 Hz SLIT: 2 mm / 2 mm GATED DELAY TIME: 3 µs GATE TIME: 50 µs

1.2 × 104

Detector: NIR-PMT R5509-43

5-ALA (Photosensitizer)

50

SAMPLE TEMPERATURE

In solvents which singlet oxygen has a long life, there is little singlet oxygen that thermally disappears so more singlet oxygen disappears during the emission process. This results in an increase in the entire emission level.

Sample

40

TIME (µs)

INTEGRATED COUNTS (100 SHOT)

Singlet oxygen lifetime can be measured with high accuracy, by using gated photon counting techniques that utilize high-speed response of a near infrared PMT and allow continuous scan of signal pulses obtained in a short gate time (sampling time).

EXCITATION LIGHT: PULSE SHG Nd: YAG (532 nm) 2.5 mJ, PULSE WIDTH: 10 ns, 20 Hz SLIT: 2 mm / 2 mm GATE (sampling) TIME: 1 µs

PHOTON COUNTS

Singlet oxygen

SAMPLE TEMPERATURE INTEGRATED COUNTS (500 SHOT)

Sample

1200 1000 800 600 400

80

60

40

20

200 0

80 mW/cm2 160 mW/cm2 240 mW/cm2

0

80 mW/cm2 160 mW/cm2 240 mW/cm2

TPMHB0786EA

Data courtesy of: Junkoh Yamamoto, Department of Neurosurgery, University of Occupational and Environmental Health, Japan Toru Hirano, Photon Medical Research Center, Hamamatsu University School of Medicine, Japan

Detector: Detector equivalent to the H10330A-45 NIR-PMT module Subject to local technical requirements and regulations, availability of products included in this promotional material may vary. Please consult with our sales office. Information furnished by HAMAMATSU is believed to be reliable. However, no responsibility is assumed for possible inaccuracies or omissions. Specifications are subject to change without notice. No patent rights are granted to any of the circuits described herein. ©2009 Hamamatsu Photonics K.K. WEB SITE www.hamamatsu.com HAMAMATSU PHOTONICS K.K., Electron Tube Division 314-5, Shimokanzo, Iwata City, Shizuoka Pref., 438-0193, Japan, Telephone: (81)539/62-5248, Fax: (81)539/62-2205 U.S.A.: Hamamatsu Corporation: 360 Foothill Road, P. O. Box 6910, Bridgewater. N.J. 08807-0910, U.S.A., Telephone: (1)908-231-0960, Fax: (1)908-231-1218 E-mail: [email protected] Germany: Hamamatsu Photonics Deutschland GmbH: Arzbergerstr. 10, D-82211 Herrsching am Ammersee, Germany, Telephone: (49)8152-375-0, Fax: (49)8152-2658 E-mail: [email protected] France: Hamamatsu Photonics France S.A.R.L.: 19, Rue du Saule Trapu, Parc du Moulin de Massy, 91882 Massy Cedex, France, Telephone: (33)1 69 53 71 00, Fax: (33)1 69 53 71 10 E-mail: [email protected] United Kingdom: Hamamatsu Photonics UK Limited: 2 Howard Court, 10 Tewin Road Welwyn Garden City Hertfordshire AL7 1BW, United Kingdom, Telephone: 44-(0)1707-294888, Fax: 44(0)1707-325777 E-mail: [email protected] North Europe: Hamamatsu Photonics Norden AB: Smidesvägen 12, SE-171-41 SOLNA, Sweden, Telephone: (46)8-509-031-00, Fax: (46)8-509-031-01 E-mail: [email protected] TPMO1040E02 Italy: Hamamatsu Photonics Italia S.R.L.: Strada della Moia, 1/E, 20020 Arese, (Milano), Italy, Telephone: (39)02-935 81 733, Fax: (39)02-935 81 741 E-mail: [email protected]

SEPT. 2009 IP