Atomic Layer Deposition (ALD)

Atomic layer deposition (ALD) is a process that is ideally suited for producing
highly conformal layers of thin films with single atomic layer thickness control. We
have been investigating use of this technique for deposition of a wide range of thin films
since 1993 with Microchemistry’s F-120 reactor. The basic ALD process is firs outlined
below and then we present some of our results of growth of semiconductor (including
quantum structures), insulator and metal films, as well as nanostructures.
Atomic layer deposition is a monolayer stepwise growth process that exploits the
binding energy difference between chemisorption and physical adsorption [1]. In this
unique technique, self-limiting growth characteristic is due to the strong interaction
between the initial layer of atoms or molecules of a reactive species and the surface
leading to chemisorption. All subsequent layers will adhere to the surface less strongly
(physisorbed). For these surface reactions, the temperature of the substrate is an
important controlling parameter. If the substrate surface is heated sufficiently, then one
can achieve a condition such that only the chemisorbed layer remains attached to the
surface and the rest of the physisorbed layers can be flushed out with an inert gas. Hence
the growth proceeds by exposing the substrate surface alternately to the precursors and
following each reaction, the excess (physisorbed) species are removed with a nitrogen
pulse. Therefore, unlike CVD, in ALD the precursors are introduced on the substrates
separately. The reactant source pulses are separated by pulses of an inert gas. Under
properly adjusted experimental conditions all the surface reactions are saturated, making
the growth process self controlled. As a result, ALE is capable of depositing conformal
films whose thickness can be determined accurately by the number of deposition cycles.
For example, this technique has been employed to coat porous alumina membranes,
porous silicon, and powders of silicon and alumina [2-5]. In addition, the separate dosing
of precursors provides that no detrimental gas-phase reactions will take place. In practice
it has been observed that the temperatures needed for depositing high quality films by
ALD are lower than those required by other methods due to the growth process driven by
surface chemistry.
The source for the reactant atoms or molecules in this process can be either solid,
liquid (with relatively high vapor pressure) or gas. The film grows stepwise, i.e., a single
monolayer per pulse, provided that at least one complete monolayer coverage of an
element or a chemical compound is formed before the next pulse is allowed to react with
the surface. Any excess incident atoms or molecules on the film will not stick if the
substrate temperature is properly chosen. Therefore, with proper optimization of the
deposition parameters a self-limited, saturated monolayer coverage is obtained per cycle
which distinguishes ALD from other vapor phase deposition techniques, namely MBE
and CVD. For this reason the name digital epitaxy has also been used to describe the
monolayer per cycle growth.
The deposit thickness is expressed in terms of the number of cycles employed. Each
cycle comprises a pulse of each source beam. The source beam is turned off for a
sufficiently long time (a fraction of a second to several seconds) after each pulse to allow
the surface to approach thermodynamic equilibrium at the end of each reaction. This step
entirely eliminates fluid dynamics (e.g., gas flow rates) from the growth process and
allows uniform film growth over large substrates.
 Currently we are using this technique for deposition of high dielectric constant (high
k) thin gate oxides, Cu films (including filling of trenches and vias), for fabrication of
electroluminescent devices (e.g., SrS: Cu), and nanowires.

High-k dielectrics.
The table below shows the dielectric properties of some of the high-k dielectrics we
have investigated.

k Band gap (eV) CB offset (eV)

HfO2 16 6 1.5
ZrO2 21 5.8 1.4
Ta2O5 27 4.4 0.3

Thin films composed of alternating layers of these dielectrics display distinctly different
dielectric properties. One of these properties is the reduced leakage current as shown
below.

-3
10

-4
10
Current density (A/cm2)

-5
10 SiON T=3.2 nm
Ta2O5-HfO2 Teq=2.65 nm
10
-6 Ta2O5-ZrO2 Teq=2.7 nm
ZrO2-HfO2 Teq =2.3nm
-7
10

-8
10

-9
10

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
Gate Bias (V)
ALD of metal films

AFM surface scans of ALD and CVD grown copper films.

ALD Cu Film (Continuous; larger mean CVD Cu Film (Coarse surface with
Grain size) excessive pitting between Grains)
 Reflection of a picture of th eSTatue
of Liberty on ALD grown copper
film

ALD grown copper as a seed layer for electrodeposition of copper trenches.

20 nm thick ALD seed layer

Electrodeposited copper on the seed

layer.
 ALD of superlattice nanowires
(15 layers of ZnSe + 5 layers of CdSe)

ZnSe

Lattice constants (111)

Meas. Bulk
ZnSe 0.33 nm 0.327nm CdSe
CdSe 0.35 nm 0.349nm

ZnSe

CdSe
(Marker: 5nm)

SEM view of the superlattice nanowire TEM micrograph showing the

ZnSe/CdSe superlattices

ALD of thin films for electroluminescent displays

ALD was developed in Finland by Professor Suntola’s group to fabricate thin film
electroluminescent (TFEL) flat panel displays. These displays have superior
performance in terms of compact size, wide viewing angle, good image quality with high
contrast and resolution, solid state ruggedness, and fast response time over a wide
temperature range in comparison to the widely used liquid crystal based flat panel
displays. Sizes ranging from giant screens to miniaturized active matrix head mounted
EL displays have been produced for both commercial and high performance military
applications. Multi-color displays based on ZnS phosphor doped with Mn (yellow
emission) and Tb (green emission) have been produced with ALD since the mid 1980’s
in large scale by Planar International Corporation for advanced industrial and medical
instrumentation markets.
The TFEL structure consists of a light-emitting sulfide based phosphor film
sandwiched between two oxide based dielectric films with conducting layers grown over
either a glass substrate or Si wafer. The phenomenon of EL is mainly based on the non-
thermal conversion of electrical energy into luminous energy by electron excitation of
luminescent activators or dopants in the bulk phosphor films. When a large enough
electric field (1.5MV/cm) is applied across light emitting phosphor layer through the
adjacent dielectric films, typically composed of mixed Al2O3-TiO2 or Ta2O5, any
imperfections (pin holes in the dielectric, film non-uniformity or crystal defect in the
phosphor) in the thin film stack would result in poor luminous efficiency and a
degradation of display characteristics. The ALD technology has been used in production
environments to grow effective dielectric and bright phosphor films with no pinholes and
high uniformity over large area panels in one fully automated run.
ALD process has been developed for growing ultra-thin film structures over
embedded information carrying sensitive devices on Si substrates. Excellent conformal
coating of TFEL stack materials with very few pinhole defects over uneven topographical
features of the IC devices has been realized in superior display performances and
reliability. By choosing appropriate host material and dopants, full color EL displays can
be produced.

Quantum well electroluminescent displays

Traditional EL phosphor materials consist of either donor/acceptor doped semiconductors

(so-called non-characteristic phosphors) or of relatively high band gap semiconducting
(insulating) materials that are doped with luminescing impurity ions (so-called
characteristic phosphors). Both types are widely used for cathodoluminescence (CL), a
mature technology for CRT displays. We have demonstrated an entirely new class of
artificially engineered phosphors in which deep quantum wells (QWs) embedded in high
band gap material act as efficient radiative recombination centers by effectively trapping
electrons and holes for subsequent recombination. The concept was proved in a
CdSe/SrS and ZnSe/CaS MQW systems prepared by atomic layer deposition (ALD) on
glass substrates. One should note that CdSe and ZnSe QWs were fabricated in SrS and
CaS polycrystalline grains, respectively.
To verify that the emission observed was indeed from the recombination of trapped
electrons and holes, energy levels of the QW structures were first determined using the
finite well model. There was a good agreement between the measured emission
wavelengths and the calculated values.

Band offsets of the CdSe/SrS MQWEL phosphor ~under bias

Ref : R. Engelmann, J. Ferguson, and R. Solanki, Appl. Phys. Lett. 70, 411 (1997)
 Electroluminescence from diatoms.
Many living organisms fabricate intricate biogenic silica materials that possess optical
and photonic properties. For example, diatoms are a prolific class of single-celled algae
which fabricate silica shells called “frustules” that possess periodic submicron scale
features, including two-dimensional pore arrays. Preliminary calculations suggest that the
diatom frustule can act as a photonic crystal to provide resonances in the visible spectral
range. Diatom cells fabricate these periodic structures from soluble silicon by a bottom-
up, self-assembly process involving silica nanoparticle building blocks. An SEM and a
TEM image of a representative biosilica frustule from the diatom Pinnularia sp. are
shown below.

SEM view of Pinnularia sp. Frustule

Diatom frustules were used to fabricate electroluminescent device shown in Fig. 2.

The photoluminescence (PL) and electroluminescence (EL) spectra for Pinnularia sp.
frustules bearing 1.6 wt% Ge in the biosilica within this device are compared in Fig. 3.
The PL spectrum was continuous, with peak wavelength of 451 nm and half-maximum
peak width of 142 nm. In contrast, the EL spectra consisted of a series of sharp line
emissions. Obviously, there are two different mechanisms for PL and EL emission.
While the origin of PL is most likely due to interaction of light (of 3.68 eV) with surface
defects on of the frustule biosilica, the EL results from higher energy (150 V) electronic
excitation of the defect centers within the bulk of the frustules and the interaction of light
with the periodic holes, i.e., the frustule behaves as a two-dimensional photonic crystal.
Optical modes of such a the diatom photonic crystal were modeled where the geometrical
parameters were taken from scanning electron and transmission electron microscope
pictures of the frustules valve. These emissions were consistent with our photonic crystal
calculations.
 6000

5000

Intensity (arb. units)

4000

3000

2000

1000

0
300 400 500 600 700 800 900
Wavelength (nm)

PL (blue continuous line) and EL (pink spikes) emission from the diatom EL device

Calculated TE band structure for diatom periodic structure.