Development of the Electrochemical Solution Growth (ESG) Technique for Native GaN Substrates

DOE Energy Storage & Power Electronics Research Program 30 September 2008 PI: Karen Waldrip
Advanced Power Sources R&D, Dept 2546

PM: Stan Atcitty, John Boyes

Sandia National Laboratories, Albuquerque, NM, 87185

Sponsor: Gil Bindewald, DOE Power Electronics & Energy Storage Program
Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energys National Nuclear Security Administration under contract DE-AC04-94AL85000.

Outline

Motivation Existing GaN Growth Technique Epitaxial Lateral Overgrowth Methods for Growing Bulk GaN Development of the Electrochemical Solution Growth Technique Electroplating GaN from Ga+3 and N-3 Electrochemical Solution Growth (ESG) Initial Results

Project Objective

To develop a novel, scalable, cost-effective growth technique for producing high quality, low dislocation density bulk gallium nitride for substrates for GaN-based power electronics.

Project Start: 5/08 Previous Funding: DOEs Solid-State Lighting

Combined Figure of Merit

K (W/cmC) Ec (MV/cm) Si SiC GaN 1.31 4.9 1.3 0.3 2 3.3

11.8 10 9

(cm /Vs) 1350 650 1200

vs 1 x 10 7 2 x 10 7 2.5 x 10
7

Combined Figure of Merit 1 136 153

Energy gap - lattice parameter diagram of III-nitrides

6.0 5.5 5.0

AlN

0.2

Energy Gap (eV)

4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 3.0 3.1 3.2 3.3 3.4 3.5 3.6 0.3

GaN
0.4 0.5

InN 2.4% tension 11% compression

1.0

2.0 5.0

In-plane Lattice Constant a ()

Wavelength (m)

Heterostructure Rectifiers Offer Improved Breakdown Voltages

9.7 kV for Al0.25Ga0.75N Leakage current due to bulk defects

GaN is Grown Heteroepitaxially on Sapphire (and Silicon Carbide) Substrates

As grown GaN nucleation layers contain disordered GaN with many stacking faults. Once annealed, wurtzite GaN forms on top of disordered GaN NL, forming nano-sized GaN nuclei from which further high temperature GaN growth occurs.

Figure from Lada et al., J. Crystal Growth 258, 89 (2003).

High temperature growth on the GaN nuclei produces GaN grains. Growth conditions can be varied to enhance the pyramidal growth mode or lateral coalescence. Dislocations are bent laterally on pyramidal facets. Dislocations are concentrated in bunches located microns apart.

Methods for growing bulk GaN

Dislocation Filtering Techniques
Lateral Overgrowth

True Bulk Techniques

High Nitrogen Pressure Ammonothermal growth

HVPE GaN layer

Sapphire Substrate Liftoff process P = 105atm T = 1500C t = 100 hr h = 100 m

T1

Nutrient Basket

T2 T1< T2

Seeds/ Crystals

KNH2 + GaN + 2NH3 KGa(NH2)4 GaN + 2NaNH2 + 2NH3 Na2Ga(NH2)5

GaN layer
Polishing

15 mm

GaN layer

Dislocation density = 102cm-2

4,000 5,000 atm T = 400 800oC G.R. = 50 m/day Multiple seeds

Desires/Requirements for a Bulk Growth Technique

Good crystalline quality ( 1x105cm-2) High growth rate (~mm/hr): high throughput, high volume production Low impurity content Scalable Controllable Manufacturable Reasonably inexpensive Applicable to InN, GaN, AlN, and III-N alloys

1/2N2 + 3e- N-3: The Reactive Intermediate

T. Goto and Y. Ito, Electrochemical reduction of nitrogen in a molten chloride salt Electrochimica Acta, Vol. 43, Nos 21-22, pp 3379-3384 (1998). Found that nitrogen was continuously and nearly quantitatively reduced to nitride ions
N2 gas IN N2 gas OUT (RGA)
Power Supply

Advantages of using N2 gas:

Clean Inexpensive Control over precursor conc. Continuous, controlled supply

Cathodic Reaction 1/2 N2 + 3e- = N3-

Anodic Reaction N3- = 1/2 N2 + 3e-

N3N3-

N3N3N3-

N2 ON

N3-

Molten LiCl-KCl + Li3N 450C

N2 OFF

Report of nitride concentration in LiCl in literature: 12 mole %

Initial Experimental Setup: Unseeded Growth of GaN in a Test Tube

Li3N or (Li3N + N2) + Ga, 450C, current sweep, 2 hours
Potentiostat Ni cathode Quartz tube Pt/Ga or Mo/Ga anode

120o

LiCl-KCl Li3N, 450C

N-3

Furnace coils

Produced numerous wurtzite GaN crystals; This crystal was ~1.25mm long x 0.8mm wide Ga Ga+3 + 3eGa+3 + N-3 GaN 3Li+ + 3e- 3 Li

Ga(l)

GaN ESG Produces Photoluminescent GaN Crystallites

1000
362.2 nm

325 nm 5 mW CW pump
DNZ00652C GaN Epilayer on Sapphire G15 GaN sample

PL Intensity (arb. units)

100

10
372.3 nm

1
1000
[KW-G15.raw] [KW-G15.raw]KW-G15 KW-G15
7500 7500

362.4 nm

266 nm 1 mW pulsed pump

DNZ00652C GaN Epilayer on Sapphire G15 GaN sample

Intensity(Counts) Intensity(Counts)

5000 5000

TG = 450oC PG = 1 atm

PL Intensity (arb. units)

100
366.8 nm

10

2500 2500

0.1
00 01-074-0243> 01-074-0243>GaN GaN- -Gallium GalliumNitride Nitride

300

350

400

450

500

550

600

650

20 20

30 30

40 40

Two-Theta Two-Theta(deg) (deg)

50 50

60 60

70 70

80 80

Wavelength (nm)

Mary Crawford, SNL

GNOEM Systems, Inc. Boulder Creek, CA

New Growth Technique: Electrochemical Solution Growth (ESG)

Potentiostat

Use salt flow to deliver precursors

Spinning Motor N2

Increase growth rate through flux of reactants (increase spin rate)

GaN boule

Half-reaction 1: 1/2N2 + 3e- N-3 N-3 concentrations ~12 mole % Half-reaction 2:

N-3 Ga+3

Ga Ga+3 + 3e Ga+3 equilibrium concentrations ~1 mole %

Precursors can be replenished as they are consumed Advantage: Continuous, isothermal or steady-state growth
U.S. Patent filed April 11, 2005

Example of Nitrogen Gas Reduction Cyclic Voltammograms

1/2N2 + 3e- N-3

200mV/sec

SEM of RD-ESG Growth Run #1

MOCVD-grown GaN

0.3

8 =

48 0

nm

Ga, Al-containing layer

Film surface
SIMS revealed the layer to be a graphitic carbon layer, with Ga, N, and GaN clusters GaN content was about 10% Profile was consistent with an increasing concentration Problem with salt purity from supplier Working it out with supplier Developing in-house purification technique for reagent grade salt

Industrial Partner (GNOEM) Hardware Development

First GNOEM RD-ESG Experiment

Hardware failure susceptor sheared, not sure when Black line on sample surface delineated a higher, specular region and lower, roughened area Defect selective etching observed (several microns/hr) Highly encouraging for crystal quality Must identify the conditions under which this takes place Polished cross sections of control and experiment sample consistently measure about 1m thicker for experiment

ESG-22 epoxy Control

5.907 m 7.011m

Growth Rate vs. Rotation Speed Concentration Growth and Rate vs. Rotation Speed and Concentration
100

10 mole %
Growth Rate (mm/hr)
10

1 mole %
1

0.1 mole %
0.1

1.00E+19 1.00E+20
0.01 0 2000 4000 6000 8000

1.00E+21
10000 12000

Rotation Rate (rpm)

Summary: Path For Development

Demonstrate that chemistry is viable Kinetics and thermodynamics are favorable in this setup Check for dissolution and precipitation approach Develop N2 electrochemical reduction methods Develop initial fluid dynamics schemes Deposit GaN on a seed crystal Improve crystal quality Optimize growth rate

Acknowledgments

Jeff Tsao Tom Kerley Frank Delnick David Ingersoll Bill Averill Bob Biefeld Mike Coltrin Ryan Egidi National Energy Technology Laboratory/Energy Efficiency and Renewable Energy Office of Solid-State Lighting

Paul Butler Tom Wunsch Dan Doughty Randy Creighton Christine White Dan Koleske Dave F. Smith George Antypas Mary Crawford Bertha Montoya