Background Story of

the Invention of
Efficient Blue InGaN
Light Emitting Diodes
SHUJI NAKAMURA
S O L I D S TAT E L I G H T I N G A N D E N E R G Y E L E C T R O N I C S
CENTER
M AT E R I A L S A N D E C E D E PA RT M E N T S
U N I V E R S I T Y O F C A L I F O R N I A , S A N TA B A R B A R A ,
U.S.A.

2014 NOBEL LECTURE IN PHYSICS

 Outline

1) Introduction: What is an LED?

2) Material of Choice: ZnSe vs. GaN

3) The Beginning: GaN on Sapphire

4) Enabling the LED: InGaN

5) Historical Perspective
The LED
ENERGY EFFICIENT WHITE LIGHT
 What is an LED?

A Light Emitting Diode (LED) produces light of a single color by

combining holes and electrons in a semiconductor.

Source of Holes
(p-type Layer)

External Light Out

Source of
Electrons
(Battery) Combining of
Holes and Electrons
(Active / Emitting Layer)

Substrate Source of Electrons

(Foundation) (n-type Layer)
 What is an LED?

A Light Emitting Diode (LED) produces light of a single color by

combining holes and electrons in a semiconductor.
Actual Blue LED Packaged Blue LED

Size: 0.4 mm x 0.4 mm

 White LED: Combining Colors

White Light: Blue + Other colors (red, yellow, green)

Other Colors: Convert Blue LED Light to Yellow using Phosphor.

Blue LED Phosphor White Light White LED

Convert: = Blue + Yellow
Blue → Yellow

S. Pimputkar et al., Nature Photonics 3 (2009) 180—182

 Applications for InGaN-Based LEDs

Solid State Lighting Decorative Lighting Automobile Lighting

Displays Agriculture Indoor Lighting

 Energy Savings Impact
~ 40 % Electricity Savings (261 TWh) in USA in 2030 due to LEDs
Eliminates the need for 30+ 1000 MW Power Plants by 2030
Avoids Generating ~ 185 million tons of CO2

Sources: www.nobelprize.org, US Department of Energy

1980s:
ZnSe vs. GaN
II-VI VS . III-N IN THE LATE ‘80S
 Candidates for Blue LEDs: ZnSe vs.
GaN
Semiconductors that possess the required properties
to efficiently generate blue light: ZnSe and GaN

BUT … How does one create ZnSe / GaN?

Single crystal growth of material on top of different, available single crystal:

Dislocation /
Defect

ZnSe GaN

Al2O3
GaAs
(Sapphire)

0 % Lattice Mismatch 16 % Lattice Mismatch

Few Dislocations (Defects) Significant Dislocations (Defects)
 GaN on Sapphire: Heavily Defected

Too many
Dislocations/
Defects

GaN

Sapphire
1 µm (Al2O3)
Cross section Transmission Electron Microscope (TEM) of GaN on Sapphire, F. Wu et al., UCSB
 1989: ZnSe vs. GaN for Blue LED

ZnSe on GaAs Substrate

◦ High Crystal Quality: Dislocation density < 1x103 cm-2
◦ Very Active Research: > 99 % of researchers

GaN on Sapphire Substrate

◦ Poor Crystal Quality: Dislocation density > 1x109 cm-2
◦ Little Research: < 1 % of researchers

Interest at 1992 JSAP Conference:

◦ ZnSe – Great Interest: ~ 500 Audience
◦ GaN – Little Interest: < 10 Audience
◦ GaN Actively Discouraged:
◦ “GaN has no future”
◦ “GaN people have to move to ZnSe material”
 1989: Starting Point of Research

Seeking to get Ph.D. by writing papers

◦ Very few papers written for GaN
◦ Great topic to publish lots of papers!

Working at a small company:

◦ Small Budget
◦ One Researcher

Commonly accepted in 1970s—1980s:

◦ LEDs need dislocation density < 1x103 cm-2

Never thought I could invent blue LED using GaN…

Development of
GaN
G A N MATURES
 MOCVD GaN before 1990s

MOCVD Reactor MOCVD System:

◦ High carrier gas velocity:
~ 4.25 m/s
◦ Poor uniformity
◦ Poor scalability
◦ Poor reproducibility
◦ Poor control

AlN Buffer Layers:

◦ Crack free GaN growth
◦ High Structural Quality GaN

But …
◦ Al causes significant problems
in MOCVD reactor, undesired
H. Amano, N. Sawaki, I. Akasaki, Y. Toyoda,
Appl. Phys. Lett., 48 (1986) 353—355
 Invention: Two-Flow MOCVD
1991: S. Nakamura et al., Appl. Phys. Lett., 58 (1991) 2021—2023

Invention of Two-Flow MOCVD System

(MOCVD: Metal-Organic Chemical Vapor Deposition)
Reproducible, uniform, high quality GaN growth possible
Low carrier gas velocity: ~ 1 m/s

Schematic of Two-Flow MOCVD Main Breakthrough:

Subflow to gently “push” gases down
and improve thermal boundary layer
 First MOCVD GaN Buffer Layer
1991: S. Nakamura, Jpn. J. Appl. Phys., 30 (1991) L1705—L1707

Hall Mobility vs. GaN Thickness

GaN Buffer Layer on
Sapphire substrate:
High Quality GaN Growth
Smooth and Flat Surface
over 2” Substrate

Highest Hall mobilities

reported to date:
No Buffer: 50 cm2/V s
AlN Buffer: 450 cm2/V s
Two- No Buffer: 200 cm2/V s
Flow GaN Buffer: 600 cm2/V s
 Passivation of p-type GaN
1992: S. Nakamura et al., Jpn. J. Appl. Phys., 31 (1992) L139—L142
1992: S. Nakamura et al., Jpn. J. Appl. Phys., 31 (1992) 1258—1266

Discovery: Hydrogen (H+) is source of passivation of p-type GaN

As grown MOCVD GaN contains significant hydrogen concentrations:

MOCVD Growth Gases

NH3 contains NH3

H+

Mg GaN:Mg
H with Mg-H Complex
(not p-type, highly resistive)
 Thermal Annealing of p-type GaN
Prior: Everyone annealed in H+ containing environment: no p-type GaN
Thermal Annealing in H+ free environment: p-type GaN, Industrial Process Compatible

Thermal Annealing in N2 Resistivity of MOCVD GaN:Mg vs. T

N2 Not p-type GaN

H2

Mg
HH

p-type GaN
 GaN Based Diodes
p-n GaN Homojunction
Needed
p-GaN
◦ Tunable Colors
n-GaN
Buffer
◦ Efficient Device Structure
Layer Sapphire ◦ Output Power > mW

p-n GaN Homojunction

(as developed by Akasaki & Amano)

◦ Good Crystal Quality

◦ Very Dim Light Production Double Heterostructure
◦ Very Inefficient (Z.I. Alferov & H. Kroemer,
2000 Nobel Prize in Physics)
◦ Output power << mW
◦ Cannot tune color Confines carriers, yielding
higher Quantum Efficiencies
Not Suitable for LEDs
 Homojunction vs. Double
Heterostructure
Energy Band Diagrams
Homojunction LED Double Heterostructure LED

p-type Active n-type

p-type n-type
Layer

Internal Quantum Efficiency

Auger

Shockley-Read-Hall (SRH) Spontaneous Emission

Double heterostructures increase carrier concentrations (n) in the active layer

and enhance radiative recombination rates (more light generated).
Development of
InGaN
ENABLING THE HIGH-EFFICIENCY LED
 InGaN: At the Heart of the LED
GaN Double Heterojunction (DH) InGaN meets DH requirements
Needed
Active Smaller, Tunable Band Gap / Color by
Layer changing Indium in InxGa1-xN Alloy

Sapphire
Significant Challenges though …
◦ Hard to incorporate Indium as high
vapor pressure (Indium boils off)
GaN DH-LED: Band Diagram ◦ Growth at substantially lower T:
◦ Poor Crystal Quality
n-GaN p-GaN
◦ More Defects, Impurities
◦ Grow thin Layer (“Quantum Well”)
Light
InGaN

◦ Need fine Control over Growth Conditions

◦ High quality interfaces / surface morphology
◦ Introduces Strain in Crystal
◦ Indium ~ 20 % bigger than Gallium
 InGaN growth in 1991
Despite numerous attempts by researchers in the 1970s—1980s, high quality InGaN
films with room temperature band-to-band emission had not been achieved.

Indium Incorporation
InGaN Growth:
◦ Poor quality at low T
◦ Low incorporation at high T
◦ Hard to control In concentration
◦ High impurity incorporation
◦ Heavily defected
Photoluminescence

InGaN Luminescence:
◦ No band-to-band light emission
at room temperature
(fundamental for any LED device)
◦ Significant defect emission
N. Yoshimoto, T. Matsuoka, T. Sasaki, A. Katsui,
Appl. Phys. Lett., 59 (1991) 2251—2253
 High Quality InGaN Layers
1992: S. Nakamura et al., Jpn. J. Appl. Phys., 31 (1992) L1457—L1459

Enabling Technology: Two-Flow MOCVD

High Quality InGaN Growth with Band-to-Band Emission
Controllably vary Indium Concentration and hence color

Wavelength vs. Indium Fraction

Photoluminescence Spectra of InGaN
Indigo
Lower In

Higher In

Violet
 First High Brightness InGaN LED
1994: S. Nakamura et al., Appl. Phys. Lett., 64 (1994) 1687—1689

Breakthrough Device with Exceptional Brightness

(2.5 mW Output Power @ 450 nm (Blue))

Optimization of thin InGaN Active Layer

InGaN/AlGaN Double Output Power vs. Current

Heterostructure LED

2.5 mW
The Blue LED is born

Source: www.nobelprize.org
1st InGaN QW Blue/Green/Yellow LEDs
1995: S. Nakamura et al., Jpn. J. Appl. Phys., 34 (1995) L797—L799

High Brightness LEDs of varying colors by increasing Indium content.

Demonstration of Quantum Wells (QWs).

Green SQW LED Electroluminescence

Quantum

43%
Indium

20%

70%
Wells Content

yellow
green
blue
 1st Violet InGaN MQW Laser Diode
1996: S. Nakamura et al., Jpn. J. Appl. Phys., 35 (1996) L74—L76

First Demonstration of a Violet Laser using multiple QWs.

Laser Structure using InGaN Light Output vs. Current

Starts to lase
Comparison InGaN vs. other LEDs

Inhomogeneous: (InGaN)
Bright (!) despite high defects
Higher currents mask
inhomogeneity effects
(valleys fill up)

Homogeneous: (GaN,AlGaN)
Dim as defects “swallow”
electrons without producing light

After: Lester et al., Appl. Phys. Lett., 66, (1995) 1249

 Possible Origins of High Efficiency
Indium Fluctuations form localized states:
Separate electrons from defects
Indium in Active Layer
Random Binomial Distribution Side View in Energy Landscape
% In

Valleys

No In Defects Light
Atom Probe Tomography, D. Browne et al., UCSB

Chichibu, Nakamura et al., Appl. Phys. Lett., 69 (1996) 4188; Nakamura, Science, 281 (1998) 956.
Historical
Perspective
PAST, PRESENT, FUTURE
Historical: LED Efficiency

InGaN DH-LED by
Nakamura et al., 1993

After: G. Craford, Philips Lumileds Lighting Company

 Contributions towards efficient blue
LED
p-type GaN activated by thermal p-type GaN activated by
annealing by Nakamura, 1991 Electron Beam Irradiation
Hydrogen passivation was clarified by Akasaki & Amano, 1989
as an origin of hole compensation

InGaN Emitting
(Active) Layer
n-type GaN
by Nakamura, 1992

Sapphire substrate

GaN Buffer by Nakamura, 1991 AlN Buffer by Akasaki & Amano, 1985
 GaN/InGaN on Sapphire Research
Year Researcher(s) Achievement
1969 Maruska & Tietjen GaN epitaxial layer by HVPE
1973 Maruska et al. 1st blue Mg-doped GaN MIS LED
1983 Yoshida et al. High quality GaN using AlN buffer by MBE
1985 Akasaki & Amano et al. High quality GaN using AlN buffer by MOCVD
GaN

1989 Akasaki & Amano et al. p-type GaN using LEEBI (p is too low to fabricate devices)
1991 Nakamura Invention of Two-Flow MOCVD
1991 Moustakas et al. High quality GaN using GaN buffer by MBE
1991 Nakamura High quality GaN using GaN buffer by MOCVD
p-type GaN using thermal annealing,
1992 Nakamura et al.
Discovery hydrogen passivation (p is high enough for devices)
1992 Nakamura et al. InGaN layers with RT Band to Band emission
InGaN Double Heterostructure (DH) Bright Blue LED (1
1994 Nakamura et al.
InGaN

Candela)
1995 Nakamura et al. InGaN DH Bright Green LED
1996 Nakamura et al. 1st Pulsed Violet InGaN DH MQW LDs
1996 Nakamura et al. 1st CW Violet InGaN DH MQW LDs
1996 Nichia Corp. Commercialization White LED using InGaN DH blue LED
 UCSB’s Vision
LED based White Light is great, Laser based is even better!

Device 60 W Incandescent External Quantum Efficiency

Equivalent LED/Laser vs. Current Density

Commercial LED & Laser

LED
LED Laser
Sapphire
28 mm2

Laser Bulk GaN 0.3 mm2

M. Cantore et al., UCSB

Phosphor
Strip
 Acknowledgements
Nichia:
Nobuo Ogawa, Founder of Nichia Chemical Corp.
Eiji Ogawa, President
Colleagues of R&D Departments in 1989—1999
All employees of Nichia Chemical Corporation

UCSB:
Chancellor Henry Yang
Dean Rod Alferness, Matthew Tirrell

Profs. Steve DenBaars, Jim Speck, Umesh Mishra