Shuji Nakamura Stephen Pearton
`Gerhard Fasol
`w 7
`
`wear-“'2;
`
` The Blue Laserw"
`
`The Complete Story
`
`Second Updated and Extended Edition
`With 256 Figures and 61 Tables
`
`
`
`Springer
`
`NICHIA EX2016
`
`NICHIA EX2016
`
`

`

`Stephen Pearton
`University of Florida
`Dept. ofMaterials Science and Engineering
`Rhines Hall, PO Box 116400
`Gainesville, FL 32611~64oo
`USA
`e—mail: spear@mse.ufl,edu
`
`Shuji Nakamura
`Materials Dept,
`University of California
`Santa Barbara CA 93106
`USA
`e-mail: ishuji@engineering.ucsb.edu
`
`Gerhard Fasol
`
`Eurotechnology Japan Ltd.
`Parkwest Building 11th Floor
`6—12—1 Nishi-Shinjuku
`Shinjuku—ku, Tokyo 160
`Japan
`e—mail: g.fasol@ieee.org
`
`ISBN 3-540-66505—6 Springer-Verlag Berlin Heidelberg New York
`ISBN 3—540—61590—3 ist Edition Springer—Verlag Berlin Heidelberg New York
`
`Library of Congress Cataloging—in-Publication Data applied for.
`Die Deutsche Bibliothek - CIP—Einheitsaufnahme
`Nakamura, Shuji:
`The blue laser diode : the complete story / Shuji Nakamura ; Stephen Pearton ; Gerhard Fasol. -
`2., updated and extended ed.. - Berlin ; Heidelberg ; New York ; Barcelona ; Hong Kong ; London ;
`Milan; Paris ; Singapore ; Tokyo : Springer, 2000 (Physics and astronomy) ISBN 3—540—66505-6
`
`This work is subject to copyright. All rights are reserved, whether the whole or part of the material
`is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broad—
`casting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of
`this publication or parts thereof is permitted only under the provisions of the German Copyright Law
`of September 9, 1965, in its current version, and permission for use must always be obtained from
`Springer—Verlag. Violations are liable for prosecution under the German Copyright Law.
`
`Springer—Verlag Berlin Heidelberg New York
`a member of BertelsmannSpringer Science+Business Media GmbH
`
`© Springer—Verlag Berlin Heidelberg 1997, 2000
`Printed in Germany
`
`The use of general descriptive names, registered names, trademarks, etc. in this publication does not
`imply, even in the absence of a specific statement, that such names are exempt from the relevant pro—
`tective laws and regulations and therefore free for general use.
`
`Data conversion by LE TEX Jelonek, Schmidt & Vockler GbR, Leipzig
`Cover design: design 6* production GmbH, Heidelberg
`Printed on acid—free paper
`SPIN: 10695409
`57/3144/mf
`
`5 4 3 2 1 o
`
`NICHIA EX2016
`
`NICHIA EX2016
`
`

`

` j
`II
`II
`
`2.5 Key Steps in the Discovery
`
`1-
`
`
`
`Resistivity(Qcm)
`
`
`
`Annealiin NH'fi
`(NHEffilsseGiatesru
`riesumn-g atomgc
`“I'DCQEOE'5RP'SIEWEEQS.
`Il
`QCCEPthS)
`‘
`I
`
`
`
`
`
`
`10 ____________________ 1 _____
`
`
`
`100 ______;"H "; _____ :— """f' __ '"l' ''''
`l
`i
`l
`I
`I
`1
`J
`'
`I
`L
`200
`400
`600
`800
`1000
`Temperature (°C)
`
`0
`
`Fig. 2.3. For a long time it was
`thought impossible to obtain p—type
`GaN. Akasaki et al. demonstrated
`that p-type GaN can be obtained
`by electron beam annealing. Naka—
`mura finally elucidated why p—type
`GaN was never found before:
`re-
`
`searchers had always used ammonia
`for annealing which dissociates dur-
`ing the thermal. annealing. dissoci—
`ation of ammonia yields atomic hy—
`drogen which passivates the aceep—
`tors (such passivation is of course
`highly undesirable for most device
`production in this case here)
`
`— elucidation of the annealing process, and demonstration of p-type doping
`without electron beam irradiation by thermal annealing (Nakamura et all
`see Fig. 2.3)
`— two gas flow MOCVD technique (Nakamura)
`
`As research on the GaN group of materials is now rapidly scaled up at
`many laboratories throughout the world. it is expected that there will be
`rapid improvements in material quality. and possibly the development of
`alternative growth procedures.
`
`2.5.1 Research History of Shuji Nakamura and Selected Steps
`in the Development of the Commercial Blue GaN LED
`
`— 1971: Pankove (RCA, Princeton) demonstrates blue GaN metal—insulator—
`semiconductor LED
`
`— 1974: Pankove and Temple demonstrate cubic GaN
`f March 1979: Nakamura graduates from Tokushima University
`— April 1979: Nakamura enters Nichia Chemical Industries
`A 1979~19822 Nakamura refines metallic gallium for liquid phase epitaxy ap—
`plications and develops polycrystalline GaP
`— 1981: GaN MIS LED (10 milli—Candela) Akasaki and others at Matsushita
`(quantum efficiency :.. 0.12%), first flip—chip type
`— 1982 7-1985: Nakamura develops polycrystalline and single crystal GaAs
`— 1985—11988: Nakamura develops crystal growth technology of GaAlAs for
`red and infra—red light emitting diodes by liquid phase epitaxy
`
`NICHIA EX2016
`
`NICHIA EX2016
`
`

`

`16
`
`2. Background
`
`— 1986: Akasaki grows high quality (3th using a—AlN buffer layers. Mizuta
`et al. grow cubic GaN
`— 1988: Akasaki discovers p—type conducting GaN using low energy electron
`beam irradiation
`
`— March 198877March 1989: Nakamura works as visiting research associate
`at
`the University of Florida (Professor Ramaswamy‘s group)
`to learn
`MOCVD. Research 011 MOCVD growth of GaAs on Si
`~ April 1989: Nakamura begins research towards blue LED
`— Sept. 1990: Nakamura develops new "two—flowl MOCVD equipment for
`growth of high quality single crystal GaN layers
`— Feb. 1991: Nakamura grows high quality p—type GaN
`— 6 May 1991: Nakamura secretly publishes his first scientific article [Appl.
`Phys. Lett. Vol. 58., (1991) p. 1021] on his MOCVD equipment.
`— March 1991: Nakamura fabricates GaN pn—junction light emitting diode.
`confirms light emission
`— June 1991: 3M reports ZnSe—CdZnSe based blue semiconductor laser
`— 1992: Akasaki demonstrates GaN based blue pn—junction LED (light out
`put: 1.5 mW at room temperature. quantum efficiency: 1.5%)
`# Feb. 1992: Nakamura begins to grow InGaN single crystal layers for the
`production of double heterostructures
`— June 1992: Nakamura successfully grows lnGaN single crystal layers
`— Sept. 1992: Nakamura fabricates InGaN double heterojunction light emit—
`ting diode
`— Dec, 1992: Nakamura succeeds in fabrication of InGaN double heterojunc-
`tion light emitting diode with high light output
`— Nov. 1993: Nakamura demonstrates 1 candela InGaN blue light emitting
`diode product
`— NOV 1993: Nichia announces commercial blue InGaN LEDs
`
`~ May 1994: Nakamura demonstrates 2 candela InGaN blue green light emit—
`ting diode product
`— from 1994: Nichia employs 100 people in the commercial production of blue
`LEDs
`
`— Sept. 1995: Nichia announces commercial green InGaN based LEDs
`— Jan. 1996: Nakamura reports pulsed blue InGaN injection laser at room
`temperature
`— 1996: Nichia sells several million blue indium gallium nitride LEDs per
`month
`
`— Nov. 1996: Nakamura announces the first CW (continuous wave) blue gal—
`liuln nitride based injection laser at room temperature
`— 1991 1999: Nakamura improves laser lifetime through improved layer de—
`sign and growth (ELOG)
`~ 1999: Nichia announces sample shipment of violet InGaN laser diodes
`— 1999: Nichia announces commercial violet InGaN laser diodes
`
`NICHIA EX2016
`
`NICHIA EX2016
`
`