Quantum Well Intermixing and Its Applications

Shu Yuan School of Materials Engineering Nanyang Technological University Singapore Thanks to the following friends for providing some slides: Dr. B. S. Ooi, Phosistors Inc., CA, USA Dr. C. Jagadish & Dr. L. Fu, Australian Natl Univ. Dr. S. F. Yu, NTU & late Dr. E. H. Li (Hong Kong Univ.)

Contents
Introduction Techniques for QW intermixing Device applications Conclusions

Introduction
What is QW intermixing?
A non-square QW produced by thermal induced interdiffusion of constituent atoms through the QW heterointerface

Quantum Well Intermixing

before after 1

Column III self diffusion through a Column III interstitial mechanism.

Ga As Ga As Ga Ga As As Ga As VGa Al As As Al As IAl As As As IGa Ga As As Ga As Ga Ga As As Ga As Ga Al As As Al As Al Al As As Al As Al VAl As Al Al As As Al As

GaAs

As

AlAs

Ga

Ga

Al

Al

Ga As

Ga As

Al As

Al As

interface
As atom Al atom

Ga atom

GaAs

Before QWI

AlAs

As atom

Ga atom

Al atom

AlxGa1-xAs

After QWI

AlyGa1-yAs

Quantum Well Intermixing Techniques

Impurity Induced Intermixing
e.g., Zn diffusion induced intermixing

Impurity Free Intermixing

e.g., intermixing induced by SiO2 cap

Laser Induced Intermixing

Especially for InGaAsP/InP QW structures

QWI techniques

How to produce QWI?

By slow (hrs) / rapid (sec-min) thermal annealing (Group III atoms self-diffusion with the help of Group III interstitial and vacancy diffusion) By controlled interdiffusion using impurity or impurity-free / vacancy disordering Laser-assisted disordering

Thermal Annealing (n-Sample, p-Sample, SI sample PL results)

Transfer energy to crystal lattice increase defect migration and enhanced defect formation
12 N-sample (on Si-doped GaAs) P-Sample(on Zn-doped GaAs) 9 SI-Sample (on semi-insulating GaAs)
As-grown
100nm GaAs (undoped) 50nm Al0.24Ga0.76As (undoped) 4nm GaAs (undoped) 50nm Al0.24Ga0.76As (undoped)

Relative PL Intensity (a.u.)

RTA@880C

200nm GaAs buffer (undoped)

6
(001) GaAs substrate

0 700 720 740 760 780 800

Wavelength (nm)

Rapid thermal Annealing of GaAs/AlGaAs quantum wells

120
N-Sample

100

P-Sample SI-Sample

PL Energy Shift (meV)

80

60

40

20 RTA @ 876 C 0 0 30 60 90 120 150 180

RTA Time (s)

Diffusion equations in quantum well intermixing

The group III atom profile W across the quantum well can be described as:

where z is the displacement in the growth direction and is centered at the quantum well center, Lz is the well width, Ld = sqrt (Dt) is the diffusion length, D is the diffusion coefficient, and t is the diffusion time.

S. Yuan et al, J. Appl. Phys., Vol. 83, No. 3, 1 February 1998

Al profile of a GaAs/AlGaAs quantum well before and after intermixing.

Impurity Induced Intermixing

Zn or Si diffusion enhanced QWI

Impurity Induced Intermixing Mechanism

Si induced intermixing: The + SiGa donor binds with the Group III vacancy and they move together.
VIII

to form a

complex

+ ( SiGa VIII )

Zn induced intermixing: Column III interstitial is generated directly by an Interstitial Zn moving into a Column III lattice site through a kick-out mechanism:
++ + ZnI ZnIII + I III + 2h +

The group III vacancy and interstitial diffusion causes Column III atoms (like Ga, Al, In) to diffuse through the sample.

Ion implantation Induced Intermixing

(1) Ion implantation (2) Rapid thermal annealing

Ion implantation

Vacancy Point defects:

QW

Interstitial

Intermixing

Impurity induced intermixing: ion implantation

Ion energies from a few keV to several MeV Implant doses from 1010 to more than 1016 ions/cm2 Great combinations of ions and substrates possible, e.g. p-type ion (Zn, Be) n-type ion (Si) neutral-type ion (O) constituent ion (Al, Ga, As) on AlGaAs/GaAs

Ion implantation Induced Intermixing

Photoluminescence photon energy shift as a function of irradiation dose. RTA: 900C for 30s. 40-keV proton implantation profile in a 4-well multiple quantum well structure. H. H. Tan, C. Jagadish et al Appl. Phys. Lett. 68, 2401(1995)

Lateral Selectivity of QW Intermixing (Ion implantation induced intermixing)

MOCVD grown InGaAs/InGaAsP unstrained laser structure P+ at 1 MeV with 1014 cm-2 dose at 200 C prior to implantation, a 2.0m SiO2 layer as a selective area mask 5m mask stripe width giving a lateral selectivity of 2.5 m
J.Vac. Sci. Tech. A, vol.16, no.2 (1998)

Impurity free induced intermixing

(a) As-grown GaAs/AlAs QW

(b) A SiO2 cap layer is deposited on top of the sample. The sample is then annealed. Ga atoms are socked into the SiO2 cap, leaving behind some Ga vacancies, thus promoting interdiffusion between Al and Ga atoms.

Selective area QWI

SiO2: promotes intermixing SrF2: surpresses intermixing
S iO 2 capp ing layer

Intensity (arb. units)

1m SrF 2 ma sk

SrF2 area percentage

0% 15% 25% 50% As-grown

Up per c ladd ing Al GaAs Ga As D QW

L owe r cla ddin g AlGaAs

830

840

850
Wavelength (nm)

860

870

Vacancy diffusion front

Degree of intermixing is in some way proportional to the area of contact between the sample and the SiO2 cap. One-step lithography (e-beam), lift-off, and one-step RTP.
B.S. Ooi, et.al IEEE. J. Quantum Electron. , 33 (10), pp1784-1793, (1997)

Impurity free intermixing (Pulsed anodic oxide induced intermixing)

Pulsed anodic oxidation set-up

Pulsed anodic oxide induced intermixing Effects of the distance between the oxide and the quantum well

Impurity free intermixing application to quantum wire photoluminescence (Pulsed anodic oxide induced intermixing)

Quantum well intermixing in the side walls enhances the lateral confinement of electrons in the quantum wire, resulting in the observation of PL signal from the quantum wire (QWR).

Laser induced intermixing

Quantum Well Intermixing

Eg starting

Eg disordered

Bandgap increases as intermixing proceeds

Laser induced intermixing methods:

Direct laser radiation: thermal intermixing (poor spatial resolution ~ 100 micron ) Two step Photo-absorption induced intermixing: (1) Laser radiation at low power and low temperature to generate defects (2) High temperature annealing. (better spatial resolution ~20 micron)

Laser induced intermixing: experimental set-up

Setup consists of computer-controlled x-y table and a laser Operation: AlGaAS-GaAs as example Encapsulation layer Si3N4 (90nm) Light source Ar+ laser beam, = 488nm scan speed 85 m / s
Appl. Phys. Lett. 52, 1371 (1988)

Laser induced intermixing (pulsed photonabsorptionassisted interdiffusion, PPAID)

Power-current characteristics of three lasers As-grown, control (annealed, without pulsed laser exposure), and PPAID lasers.

Emission spectrum of these three lasers.

B. S. Ooi et al, IEEE Photonics Technology Letters, 9, 587(1997)

Quantum Well Intermixing Applications

Laser diodes: non-absorbing mirrors (windows) Laterial confinement lasers Photonic Integration

Nonabsorbing mirror laser diodes

Selected area QWI
y er a l on lat i u s sP in aA G O 2 i n S s- I aA G In W Q M m Au T i/ et a nt l co act

u i/A N / act /Au /Ge co n t u A ac k b

QWI in a region near the laser facet (window/mirror) to increase the band gap of that region, making that region transparent to the laser beam, reducing the light absorption and reducing facet temperature ==> higher light output and better reliability

Lateral confinement in laser diodes

Lateral electrical and optical confinements can both be enhanced by QWI in the regions outside of the ridge wave guide. When this region is intermixing, the effective band gap is increased, and effective refractive index is reduced.

Lateral confinement in laser diodes

Lateral leakage current is reduced by impurity induced intermixing (IID). S. Y. Hu et al, PTL 7, 712(1995)

Photonic Integration Laser action occurs just above the band-edge

i.e. passive section is highly absorbing at lasing wavelength

Solution:
modify the bandgap energy at the passive region
Laser Modulator Waveguide coupler

QWs

Absorption

Laser

modulator

waveguide

Energy

Photonic integration by using QW Intermixing

Quantum well amplifier

Low-loss waveguide

Excellent alignment of active and passive waveguides Reflection at the joint can be negligible (~10-6) Mode matching is intrinsic to the process

Extended Cavity Lasers Two-section Integration

ser e la v i t A c ct io n se e io n siv t P as e sec d i egu wav

Active cavity = 500 m Passive cavity lengths = 0 600 m

Multiple wavelength laser array

Ion implantation
p-type contact Oxide isolation QW Substrate n-type contact

un-implanted

dose A

dose B

dose A < dose B 1 > 2 > 3

Multiple wavelength laser array (results)

As-grown Control
1.6

Threshold Current Density (kA/cm2)

As-grown Control
Intensity (a.u)

Intensity (a.u)

1.4 1.2

1e14 cm As 1e14 cm P
-2

-2

++

++

1e14cm As

1e14cm P

1e12cm As

++

-2

-2

-2

++

++

1.0

0.8

0.6

1400 1420 1440 1460 1480 1500 1520 1540 1560

0.0

0.1

0.2

0.3

0.4

0.5

0.6

Wavelength (nm)

Current (A)

< 20% increase in Jth, and <10% increase in slope efficiency for 140 nm bandgap tuned lasers.

Multiple Wavelength Integration Capability

0.005

Enveloped curve

PL intensity (a.u.)

0.004

0.003

FWHM=113 nm

0.002

0.001

0.000

1250

1300

1350

1400

1450

1500

Wavelength (nm)

Multiple bandgaps monolithically integrated on a single chip Wavelength spans over entire C-band
Confidential

Multiple-Bandgap Integration
Ion-Implantation Induced Disordering

SiO2

Semiconductor wafer

One-step implantation, one-step RTP, multiple-step of lithography and dry etching.

E.S. Koteles, et. al, IEEE Selected Topics in Quantum Electron, 1998

One-Step Multiple-Bandgap Integration

Photoresist SiO2

SiO2

Semiconductor wafer

Semiconductor wafer

One photolithography step to achieve different thickness of resist. One dry etching step to create different thickness of SiO2 implant mask. One implantation and RTP step to create multiple bandgap across a laser chip.
B.S. Ooi, et. al, Multiple Bandgap Photonic Integration, PTC Patent pending, 1999

Monolithic Multiple Wavelength Lasers

I so

lat i

on
La se c ser t io n

Multiple wavelength lasers (10-channel) fabricated using the one-step postgrowth bandgap engineering technique.
B.S. Ooi, et. al, A technique for fabricating WDM laser sources, PTC Patent pending, 2000

Monolithic Multiple Wavelength Lasers

Lasing wavelength (nm)

1560 1540 1520 1500 SiO2 thickness 1480 1460 1 2 3 4 5 6 7 8 9 10 Lasing wavelength

SiO2 thickness (nm)

0.6 0.4 0.2 0.0

Channel number

Intensity (a.u.)
1470 1480 1490 1500 1510 1520 1530 1540 1550 1560

0.8

Wavelength (nm)

A correlation between SiO2 thickness and the emission has been observed. 17% increase in Jth, i.e. from 1.2 kA/cm2 (channel 1) to 1.4 kA/cm2 (channel 10). Only small change in slope efficiency has been observed.

Tuning the wavelength of QWIP

Metal contact Top contact Multi-QWs Metal contact Bottom contact Substrate

un-implanted

dose A

<

dose B

1 < 2 < 3

Conclusions
Quantum well intermixing: post-growth modification of band gap ==> usually larger band gap (0-200meV) and lower refractive index (0-5% change)

Impurity induced intermixing Impurity free vacancy induced intermixing Laser induced intermixing
Its applications

Improving device performance Photonic integration Vielendank !