Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech.
Development and Application of Brand-new Atmospheric Plasma Sources
Okino Lab. FIRST, Tokyo Institute of Technology
© 2008- Akitoshi Okino, All rights reserved. Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. What is plasma ? Plasma is the fourth state of matter
A simple plasma consists of positive ions, electrons, excited atoms and radicals,,, in a sea of neutral atoms (molecules). The particles in the plasma are moving in random directions.
Plasma has some different electron電子 characteristics from normal gas.
イオンion
0℃ 100℃ a few 1000℃ ice water water vapor ionized gas
Solid Liquid Gas Plasma Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Plasmas around us
Natural： Lightning bolt Solar wind Aurora
Artificial： Fluorescent tube Neon sign Plasma display Xenon discharge light Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Characteristics of plasma
Reactivity Can generate dense high reactive species (radicals, ions, electrons,,). → Semiconductor processing (CVD, etching) → New material processing (CNT, DLC) Emissivity Can emit light (～FIR～IR～visible～UV～EUV～) The wavelength is depend on the gas species and the temperature → PDP, Light source, Laser, Elemental analysis
Electric conductivity Has electric conductivity and the degree is controllable (depend on the temperature) → Plasma switch High temperature Has very high temperature (over 10,000 K) (Combustion : below 3,000 K) In the nuclear fusion plasma it is higher than 10,000,000 K. → Decomposition of industrial wastes → Cutting of high melting point material, Nuclear fusion Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Generation method of plasmas
In industrial use, plasma generation method is chosen according to demand of plasma pressure, temperature, purity, kind of gas,,
◆ Discharge frequency DC ～ HF (kHz) ～ RF (MHz) ～ Microwave (GHz) or HV pulse
◆ Electrode Electrode discharge or Electrode-less discharge
◆ Pressure Vacuum ～ Low ～ Atmospheric ～ High pressure
It's very special ! Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Why atmospheric plasma is so special ?
Merits (1) Eliminate vacuum chamber, pumping system → Low cost (2) Eliminate pumping → Continuous processing (3) High density plasma → High speed processing (4) Applicable for large targets → Car, Airplane (5) Applicable for hear sensitive targets → Human skin, Foods
Low pressure Atmospheric Difficulty Plasma generation is (was) not so easy (compare with usual low pressure plasma) Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Research of atmospheric plasmas
Presentation percentage of atmospheric plasma in IEEE ICOPS (International Conference on Plasma Science).
until 2005 less than 1% 2006 Traverse City, USA 1.0% 2007 Albuquerque, USA 3.3% 2008 Karlsruhe, Germany 6.0% 2009 San Diego, USA 13.1% 2010 Norfolk, USA 25.0% 2011 Chicago, USA 26.1% 2012 Edinburgh, UK 26.4% 2018 Denver, USA more than 30%
This increasing is because of Low Temperature Plasma ! Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Atmospheric low temperature plasmas
Atmospheric plasma research has been widely spread because Low Temperature Plasma could be generated.
Barrier discharge Corona discharge Plasma bullet
Applications： Merit: ✓ Low temperature Improvement of (room temp ～ 200℃) ✓ Adhesion
✓ Paintability Problems: ✓ Limitation of target size/material Sterilization ✓ Limitation of plasma gas ✓ Temperature is not controllable Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Our atmospheric DAMAGE-FREE plasma sources PAT.P ✓ Low temperature ✓ No electric shock
Damage-free plasma
Applicable for living body/ It's touchable ! metal/plastic/paper/textile.
1m Long Line Type Plasma Jet Type Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Two problems of common low temperature plasma sources
1. Limitation of plasma gas
2. Temperature is not controllable Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Atmospheric damage-free MULTI-GAS plasma jet
Flow rate : 5 L/min Voltage : 6 kV～ Power : 6～17 W
✓ Applicable for living body/metal/plastic/paper/textile ✓ Applicable for surface treatments such as cleaning, hydrophilization, oxidation, azotizing, coating Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Irradiation of multi-gas plasma jet
✓You can touch the plasma
Paper Plastic Glass
Fluits Ice Icecream Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech.
Hydrophilization of polyimide film 3L/min, 15W, 15kHz
Before After air Ar He O2 N2
✓ Material surface is easily hydrophilized by plasma irradiation. ✓ Treatment speed is depend on the plasma gas species. Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Principle of hydrophilization ≒ Surface cleaning Plasma
Intermolecular force Remove Remove Contaminations clean!
before treatment after
Hydrophobic Hydrophilic
Contaminations on the surface are removed by reactive species. Then, the metal surface is cleaned up and hydrophilized. Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Can hydrophilize almost all materials
Rubber Acrylic resin
Glass Semiconductor
Copper Polyimide film
✓ PTFE(Teflon） Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Can hydrophilize almost all materials
Gauze （Cotton100％） Knit （Cotton100％）
Rayon Weather （Poly65％, Cotton35％）
Shading curtain Work clothes （Poly65％, Cotton35％） Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Can hydrophilize almost all materials
Cardboard Woods
Natural rubber Bamboo
Drawing paper Floor tile Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Atmospheric damage-free MULTI-GAS plasma jet
ダメージフリーマルチガスプラズマジェット PCT-DFMJ01
ハイエンドタイプのダメージフリーマルチガスプラズジェット。専 用設計のプラズマヘッドにより生成されたプラズマジェットを，直 径1mmのスポットより噴射。 高密度かつダメージフリーなプラズ マを必要とするあらゆる処理に。 ガス流量計（4本）標準装備。 Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. High speed removal of copper oxide
Carry speed 50 mm (mm/sec) 3 mm 10 Treated 50 100 No-treated 200 (Oxide)
Copper oxide ~ 10 nm 1 ~ 2 nm（Natural oxide）
Copper
✓ Max carry speed: 700 mm/sec ✓ Removal speed: 93 µm/sec Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Atmospheric damage-free LINEAR plasma source
Applications： Improvement of ✓ Adhesion ✓ Paintability Sterilization
Light weight 830g and handy Outlet slit：1mm x 335mm Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Adhesion improvement of HDPE/epoxy resin HIDEN to HIDEN adhesion test ✓ Target samples are treated under atmospheric pressure ✓ Apply epoxy resin adhesive and cure perform compress test
not glue at all good gluing ! Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech.
Application to Medical Field Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Two problems of common plasma sources
1. Limitation of plasma gas
2. Temperature is not controllable Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Sterilization of E.coli
Sterilized Not-sterilized
2010/03/15 2010/03/15
2010/03/15 2010/03/15 600 ,O2 ,O2 ,O2
2010/03/19 ,O2
600s 600s 600s 600s
2010/03/12 2010/03/12 2010/03/12 2010/03/12 60
60s 60s
2010/03/17 60s 60s
N2O N2O N2O N2O 10 CO2 1 10s CO2 1 10s CO2 CO2 1 1 10s 10s Irradiation time [sec]
2
EZ2C EZ2C EZ2C EZ2C
EZ2C s s s Ar Air N2 O2 CO2 Ar+O2 s
Plasma gas
2 2 2 ✓ Sterilization speed deeply2 depends on the plasma gas.
2 2 2 2 2 Air 2 Air 2 Air 2 Air Air Air Air Air
Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Sterilization of S.mutans Confidential
Ar
N2 O2 Ar+O2
CO2
Air Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Bactericidal effect against various bacteria Confidential
グラム陰性好気性桿菌
グラム陽性通性嫌気性球菌
グラム陰性通性嫌気性桿菌 Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Bactericidal effect against various bacteria Confidential
グラム陽性通性嫌気性連鎖球菌
グラム陰性通性嫌気性桿菌
グラム陽性通性嫌気性球菌 Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Bactericidal effect against various fungi Confidential
コウジカビ
カンジダ Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Reactive species in plasma irradiated water
HO･ 2.80 V O3 2.07 V Effective for highly resistant bacteria Ozone [ µ M] OH radical [ µ M]
1 O2 Effective for H2O2 1.77 V viable bacteria Singlet Oxygen [ µ M] Hydrogen peroxide [ µ M] Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech.
Temperature-controllable plasma PAT Japan, USA, China
water freeze in 10 seconds Start cooling
Ice ! zero ℃
Gas temperature (℃) −90℃ -90℃ plasma jet
Plasma can safely irradiated for heat- sensitive materials and living body. Time (sec)
It’s must use technique for medical/dental/biological field. Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Comparison of low temperature plasmas
It's wide range and controllable !
Temperature controllable plasma
"Real" Low temp. plasma ～ Intermediate temp. plasma
Corona discharge "Common" Low temp. plasmas Barrier discharge
Room -100 0 temp 100 200 Gas temperature (℃) Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech.
Control of the plasma gas temperature Helium, 1L/min, 15W, 15kHz
10秒のプラズマ照射で水が氷に
Controllable from below 0 ℃ to high temperature Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. 3D-Printed Multi-gas Temperature-controllable Plasma Jet
20 mm
Plasma Outlet
CO2 O2 N2
Body: 3D-printed Aluminum Air He Ar Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech.
Elemental analysis in single cell Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech.
Droplet nebulizer for single cell analysis PAT Japan etc.
Single cell is included in a single droplet using microscope.
30～ 580 µm ～ (14 pL 100 nL) Individual analysis of single cell/particle 100 µm
Nozzle tip
aqueous solution
Droplet Nebulizer head 14 pL~ Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Droplet-DIN-ICPMS
We applied the Droplet-DIN to ICP-Mass Spectrometer.
Argon ICP Sampler
Agilent HP4500
MS interface Droplet nozzle Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Element anaysis of single unicelluar algae
Pseudococcomyxa simplex
Element Absolute amount（fg）
Fe 360 Mg 92 S 63 Ca 26 Zn 0.91 Mn 0.73
Fe, Mg, Ca contained in a single cell were observed by AES. Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech.
Measurement of adhesion material on heat sensitive surfaces Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech.
Atmospheric Plasma Soft Ablation; APSA PAT Japan etc.
to Mass to Mass Sprctrometer Sprctrometer
Touchable Plasma Sample Flow
Sampling surface adhesion materials without damaging to the surface Applicable to various mass spectrometers ✓ Disease diagnostics by sweat ✓ Security at airport ✓ Quality inspection of foods/drugs ✓ Measurement of cosmetics/sebum Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech.
® Estaron Mocha Boiling point: 178℃ Gas temp: 55℃
MH+ 195.10 Caffeine 2.0 M = 194.19
1.0 [M+O]H+ 211.10
Mass Signal [count] 2MH+
m/z Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Saridon® isopropylantipyrine 150 mg B.P.：319℃ Ethenzamide 250 mg B.P.：302℃
MH+ 231.18 Ethenzamide Isopropylantipyrine M = 165.19 M = 230.31
MH+ Signal [count] 166.11 (M+O)H+ Mass Signal [count] + 247.17 2MH 461.35
m/z Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Detection of chemical weapons
National Research Institute of Police Science He gas 1,100 ml/min
Teflon
Ion trap Deposited mass spectrometer chemical warfare agent (Agilent technologies, 1100 Series LC/MSD trap) Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech.
NH3 (Blister agent) 1000 ppm in 5 µL Hexane Boiling point：143℃
C6H1235Cl3NH+ 203.93 Nitrogen mustard 3 35 37 + M = 204.53 C6H12 Cl2 ClNH 205.89
C6H1235Cl37Cl2NH+ Signal [count] Signal [count] 207.85
m/z Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech.
VX (Nerve gas) 1000 ppm in 5 µL Hexane Boiling point：298℃ VX is the most danger in nerve gas. Median lethal dose：0.1 g・min/m3
C11H26NO2PSH+ 268.05 VX M = 267.4 Signal [count]
m/z Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Isopropylantipyrine on a fingher
He gas 200 ml/min Discharge capacitor：12 µF Discharge voltage：380 V Dischrge frequency：20 Hz
Ion trap mass spectrometer
Isopropylantipyrine 50 ppm (Agilent technologies, 1100 = 0.540 µg in 10μL methanol Series LC/MSD trap) Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Measurement of isopropylantipyrine on a fingher
MH+ 231.05 Isopropylantipyrine M = 230.31 Signal [count]
m/z Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. We have a plan to apply it for human skin/cosmetics
Irradiation of low temp. plasma
to Mass spectrometer Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Agriculture (Hydroponic) by plasma bubble-up water
LED
Experimental conditions
Flow rate : 5 L/min Leaf Treatment : 2 min/day lettuce Water temperature : 25 ℃ Treatment term : 3 weeks
Gas injection Liquid fertilizer (20 L) Plasma jet Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Agriculture (Hydroponic) by plasma bubble-up water
CO2 control
air O2 Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Lettuce harvested after 4 weeks
control Air CO2 Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Direct protein introduction into plant cells
Yuki Yanagawa, Hiroaki Kawano, Tomohiro Kobayashi, Hidekazu Miyahara, Akitoshi Okino and Ichiro Mitsuhara, Direct protein introduction into plant cells using a multi-gas plasma jet, PLOS ONE, 2, 12, e0171942 (2017). Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Atmospheric multi-gas thermal plasma
✓ Can generate not only Ar but He, N2, O2, CO2, N2O, air and their mixture gas plasma in atmospheric pressure. ✓ High purity thermal plasma because it's electrode-less source.
・ High gas temp：3,000 to 8,000 K ・ High electron temp：～ 10,000 K ・ High electron number density：～1015cm-3
Only one device in the world! Anethentic gas atmospheric thermal plasma (Decomposition of Global Warming gas) RF-Generator RF load coil ～ (40MHz, 500 W ) cooling gas (air)
130mm～ long 20mm o.d. 14mm i.d.
N2O 4L/min + O2 2L/min + buffered air 4 L/min (for patient-safe exhaust) Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Atmospheric multi-gas colona device Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Atmospheric multi-gas large sized plane plasma 250 x 90 mm
air Ar He
O2 N2 CO2 Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. High power pulsed multi-gas micro plasma PAT.P ✓ Multi-gas plasma generation is possible ✓ High power drive up to 100 kW by pulsed operation ✓ Battery drive is possible ⇒ Mobile analysis/treatment ✓ Scale up is easy by two/three dimensional set up High gas temp：1,000 to 5,000 K High electron temp：〜 30,000 K High Electron number density：〜1015cm-3
500 μm
Helium Argon Neon
N2 O2 CO2 Air Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. On chip plasma source using MEMS technique
Ken Kakegawa, Ryoto Harigane, Mari Aida, Hidekazu Miyahara, Shoji Maruo and Akitoshi Okino, Development of High-density Microplasma Emission Source for Micro Total Analysis System, Anal. Sci., 33, 505-510 (2017).
Best-Paper Award for Analy cal Sciences2017 Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Multi-gas plasma generation
2.8mmφ, 0.15g, 1L/min, 1～4W
Toshihhiro Takamatsu, Hiroaki Kawano, Hidekazu Miyahara, Takeshi Azuma and Akitoshi Okino, Atmospheric nonequilibrium mini-plasma jet created by a 3D printer, AIP Advances, 5, 077184 (2015). Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Highly durable water repellency fishing lines (P-Ion)
ROCK HUNTER II
MUSLARD II
On sale in Japan/US Shooter MACHINEGUN CAST Atmospheric Plasma and Spectroscopy, Okino Lab., Tokyo Tech. Okino Lab., Tokyo Tech.
Development of original atmospheric plasma sources Multi-gas thermal plasma Multi-gas low temperature plasma Linear type plasma, Large sized plasma, Microplasma Temperature controllable plasma Application for sensing/analysis Droplet neblizer for single cell elemental analysis Measurement of surface adhesion materials; APSA Ultra high sensitive plasma detector for GC Application for medical/enviromnental field Plasma medicine (Sterilization, Blood coagulation,,,) Applicaion for Beauty/Foods/Agriculture Direct protein introduction into plant cells Decomposition of waste/hazardous gases (N2O, EOG, salin)