This is invited talk presented

by Vitaly Bondarenko at
1st Ukrainian-French Seminar
“Semiconductor-on-Insulator Materials,
Devices and Circuits: Physics,
Technology and Diagnostics” and
6th International SemOI Workshop
“Nanoscaled Semiconductor-on-Insulator
Materials, Sensors and Devices”
25-28 September, 2010
Cultural Center “Jerelo”, Kyiv, Ukraine
 ZnO films and nanocrystals
on bulk silicon and SOI wafers:
Formation, Properties and Applications
V. Bondarenko, E. Chubenko
A. Belous, V. Malyshev
Belarusian State University
of Informatics and Technical Centre
Radioelectronics, “Belmicrosystems”,
Minsk, Belarus M. Balucani Integral Corporation,
Minsk, Belarus
Rome University “La Sapienza”,
Rome, Italy
 Content

○ Introduction
- What is ZnO
- Industrial ZnO Applications
- ZnO in Electronics: Technologies
- ZnO in Electronics: Applications
- ZnO vs Si and others: Properties
- ZnO vs Si: Applications and Technological Issues
○ Integration of ZnO with Si substrates
- Motivation
- Technological requirements
- Possible solutions for ZnO & Si integration
○ Low temperature ZnO deposition
- Electrochemical
- Hydrothermal
○ Applications
○ Conclusions
 page 03/37

What is Zinc Oxide ?

Zinc oxide is an inorganic compound

with the formula ZnO.

It usually appears as a white powder,

nearly insoluble in water.

In nature ZnO occurs as the mineral

Zincite

It is one of the so-called II-VI semiconductors, and

has wide direct band gap

http://en.wikipedia.org/wiki/Zinc oxide
 page 04/37

Industrial ZnO Applications

Total world production of ZnO: Total world production of silicon:

105 tones 6·106 tones

< 0,1 %
 page 05/37

ZnO in Electronics: Technology

 page 06/37

ZnO in Electronics: Applications

 page 07/37

ZnO vs Si and others

Parameter (300 K) Si GaAs ZnO GaN α-SiC

1,12 1,42 3,35 3,45 3,05

ΔEg, eV
indirect direct direct direct direct
Luminescence
10-4 60-70 70 70-80 -
efficiency, %
Electron / Hole Hall 1600 / 8500 /
300 / 10 500 / 150 900 / 40
mobility, cm2/(V·s) 430 400

Crystal lattice cubic cubic hex hex hex

Lattice constants 3,24 3,19 3,07

5,43 5,653
а0 and с0, Å 5,21 5,19 15,11
Thermal expansion 6,51 3,17 4,3
2,6 5,7
coefficient, um·m−1·K−1 3,02 5,59 4,7
Thermal conductivity,
1,49 0,55 0,60 2 4,9
W/(cm·K)
 page 08/37

ZnO vs Si: Applications and Technological Issues

Silicon Zinc Oxide

Integrated circuitry
- MOS
- CMOS
- Bipolar
High Speed Optoelectronics
High Density Piezoeffect based devices
High Reliability SAW Devices
No LEDs No Integrated circuitry
No Piezo
Si (100 mm) – $ 15
Si SOI (150 mm) – $ 300 ZnO (25 mm) – $ 3500
 page 09/37

Integration of ZnO with Si substrates: Motivation

ZnO devices and Si devices integrated on a single die

ZnO ○ We can use the Si fab to fabricate ZnO devices
○ Lower cost of the ZnO devices
Si

Discrete Devices
ZnO
Si
Hybrid Integration
Processing Packaging

Dicing Direct integration

Si

SOI bulk Si
 page 10/37

Major Problem

Genesis of Defects in Heterostructures

and as a result

CRACK!
Integration: “Marriage” of ZnO with Si

What we do know: Marriage is result of love

(not always but ....)

Does Si love ZnO ? No !

(Si wafer is thick, ZnO layer is thin)

Does ZnO love Si ? - Yes !

(ZnO layer is thin, Si wafer is thick. It is very
convinient to “live” on the thick substrate)
 Integration: “Marriage” of ZnO with Si

What to do ?
Lets introduce buffer layer between partners !!!
What about childrens ??? (We will see !!!)

Porous silicon (PS) as a buffer layer

○ reducing mismatch stress
○ increasing adhesion
 page 11/37
How to do it, if we know what to do ?

PS PS with metal sublayer

E.B. Chubenko, V.P. Bondarenko, M. Balucani, Tech. Phys. Lett. 35 (2009) 1160.
 page 12/37

Thermal Budget Issue: When to deposit ZnO ?

Local Low T Deposition:

- electrochemical
- hydrothermal

~ 700
technological steps

Hence: Low temperature

T<200 C deposition
 page 13/37

Electrochemical deposition of ZnO on Si

ZnO can be electrochemically deposited from aqueous

solution at low temperature (T = 80°C)

BUT:
Porous silicon buffer layer due to its huge effective surface is easily
etched in hot water (T > 50°C) solution with pH > 6

How to solve the problem of PS etching:

○ protect porous silicon with thin metal layer
○ deposit ZnO from non aqueous solution
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Realization: Equipment

100 mm Si wafer
with
ZnO layer
 page 15/37

Realization: Solutions & Regimes

Solutions for ZnO deposition

Aqueous:
Base Pure water
Components 0.05 – 0.1 M of Zn(NO3)2
Deposition velocity 1 – 1.5 microns/min
Current density 2 – 10 mA/cm2
Temperature 60 – 85°C

Non aqueous:
Base DMSO
Components 0.03 M of ZnCl
0.1 M of KCl (for good conductivity)
Deposition velocity 0.1 – 0.2 microns/min
Current density 0.3 – 0.5 mA/cm2
Temperature 95 – 100°C
 page 16/37

Realization: Local Deposition of ZnO

 page 17/37

Electrochemical deposition of ZnO

from aqueous solution

ZnO formation mechanism

Step II: NO3– + H2O + 2e– → NO2– + 2OH–

Step III: Zn2+ + 2OH– → Zn(OH)2 → ZnO + H2O

T. Yoshida et al. / Thin Solid Films 451 – 452 (2004) 166–169

 page 18/37
Electrochemical deposition of ZnO
from aqueous solution

Depending on process parameters:

current density, temperature, time, concentration,
different ZnO morphology types can be obtained

needle-like prismatic porous continuous

current density
E.B. Chubenko, V.P. Bondarenko, M. Balucani, Tech. Phys. Lett. 35 (2009) 1160., J. Cembrero, D. Busquets-Mataix, Thin Solid Films 517 (2009) 2859.
 page 19/37

ZnO deposition on metal buffer layer (aqueous)

Voltammograms

Deposition potential

Current density
 page 20/37

ZnO deposition on metal buffer layer

j = 2,5 мА/см2

j = 5 мА/см2

j = 7,5 мА/см2
 page 21/37
ZnO deposition on PS buffer layer from
non-aqueous solution)

Time Cross section Top view

min

25

45
 page 22/37

ZnO photoluminescence

Electrochemically deposited ZnO shows

yellow band photoluminescence
 page 23/37
How to improve optical properties
of electrodeposited ZnO

○ Optimize parameters of electrochemical deposition

○ Deposit high-quality hydrothermal ZnO nanocrystals

using electrochemically deposited ZnO as a seed
layer
 page 24/37

Hydrothermal ZnO deposition on Si

Depending of temperature and solution

composition various structures can be
obtained

HMTA – hexamethylenetetramine

75 C 85 C 95 C

Film of prisms Prismatic columns Rosettes

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Hydrothermal deposition of ZnO on seed layer

Hydrothermally grown ZnO rods shows emissions in

both UV and visible range,
 page 27/37

Hydrothermal deposition of ZnO on seed layer

PS buffer layer with different thickness H

ZnO seed layer was electrochemically deposited

H = 1 μm H = 4 μm H = 6 μm
 page 28/37

Hydrothermal deposition of ZnO on seed layer

Same sampleses after hydrothermal treatment in

Zn(NO3)2 + HMTA solution at 85 C

H = 1 μm H = 4 μm H = 6 μm
 page 29/37

ZnO deposition into porous alumina oxide

1 μm

Al2O3
Al sputtering

ZnO

Ni
TiO2
Al anodization
Ti
Si

surface cross-section

ZnO deposition
 page 31/37

Possible Applications of ZnO grown on PS

○ Photodetectors
○ Photovoltaic cells (solar cells)
○ Betta-voltaic cells
○ Gas sensors
○ Others (scintillation counter, piezo
energy generators, nanomechanics)
 page 32/37

Photodetectors: ZnO/PS heterojunction

ZnO is transparent conductive material

 page 33/37

Photovoltaic cells: ZnO/Si heterojunction

Current / mA
Voltage / V
 page 34/37
ZnO for beta voltaic
Principle of Operation
batteries

cell pin Short circuit current / µA

Electron beam current / µA

 page 35/37

Chemical gas sensors

Porous ZnO film surface

 page 36/37

Others

High performance
Scintillation Longevity
High stopping power
counter
Wide luminescence range
(compatible with Si)

Piezo Expected characteristics:

energy generators Voltage up to 20 mV
Current up to 1 μA
 page 25/37

ZnO crystalls grown on low porosity PS

Bolt Bolt
Head Rod

Nanoscrews for Nanomechanics Nanolamps

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As a conclusion: Problems to be solved

Development of the p-type ZnO doping techniques

○ Improvement of crystalline structure of electrochemically
deposited ZnO
○ Improvements of the ZnO deposition process into PAAO matrix

Acknowledgements

This work has been funded by the Belarussian Foundation

for Basic Research under the Project 06-3029 and
by the Rice Technology S.r.l. (Italy)